Chapter 4, Part 1: Other Identifiable Exposures
Those exposures covered in Chapter 2 and Chapter 3 have received much greater attention in this report than those which are identified in Chapter 4. Since the actual exposures to the materials identified below have been confirmed or are unchallenged, the development of evidence to confirm the exposures is not required.
Chemical/Biological Warfare Pre-Treatment Drug Reaction [1]
Another area in which further research appears to be warranted is the relationship between some Gulf War Syndrome cases and the administration of the nerve agent pretreatment drug given to US troops to protect them against Iraqi gas attacks. It appears possible that the use of this nerve agent pre-treatment drug may have permanently damaged some veterans' health. In addition to research on the effects of the drug itself, the possibility that these drugs might have a synergistic effect either with other drugs, or with chemical agents or other, environmental exposure, should also be thoroughly researched.
Maj. Gen. Ronald Blanck, commander of the Walter Reed Army Medical Center, has said that, "Military intelligence reports indicated there was a real possibility that Iraqi forces would employ biological and chemical weapons; in response to that threat, anthrax vaccine and botulinum vaccine were administered." The Army also gave soldiers a course of pyridostigmine bromide pills, normally used for neuro-muscular disorders. A public interest group, the Public Citizen, had filed a suit to stop experimental drugs being used on soldiers without their consent, but in the patriotic fervor immediately before the war, the suit was dismissed. [2]
Anthrax and Botulinum Toxoid Vaccines
Maj. General Blanck has advised Committee staff that the anthrax vaccine was administered to 150,000 soldiers and the botulinum vaccine to 8,000 soldiers. [3] Both the anthrax vaccine and the botulinum toxoid vaccine were manufactured by the Michigan Department of Public Health. All of the anthrax vaccine is believed to be the same type of vaccine that has been administered to veterinarians and agricultural workers in the United States since the late 1950s and approved by the Food and Drug Administration in 1971. The botulinum toxoid, manufactured using techniques similar to those employed in the production of the tetanus toxoid, has been administered to medical and laboratory workers since the early 1970s. It is still listed as investigatonal drug (IND). These vaccines are designed to raise the body's level of antibodies should the individual come into contact with the bacteria or toxin. [4]
While immediate local and some systemic reactions are reportedly experienced with the administration of these drugs, no information was developed by Committee staff that suggests that these vaciinations have widespread long term risks. Nevertheless, the effectiveness of these drugs, their possible long term effects, and the efficacy of manner in which they were administered does merit further study. No other biological warfare defense program immunizations, other than those commonly administered to travellers, have been identified by Committee staff.
Committee staff has received reports of recurring rumors that experimental recombinant DNA (rDNA) biological defense vaccines were used by the military during the Persian Gulf War. No evidence of any rDNA vaccine immunization program has been uncovered thus far. In addition, there has been some concern raised about the fact that soldiers were told that the immunizations they received were "secret." The issue of the secrecy of the vaccines is one that relates to the need to deny the enemy knowledge of those materials against which your forces have been protected, rather than to the vaccines themselves. [5]
Pyridostigmine Bromide (Group III)
During House of Representative hearings in 1993, Carol Picou, assigned to a combat support hospital during the Gulf War, recalled that when the ground war began, "we were ordered to take the drug pyridostigmine to protect us against chemical attack. Within one hour of taking the drug, I began to experience serious side-effects, such as uncontrollable twitching eyes, runny nose, excessive frothing from the mouth, neck and shoulder pain." [6] Dr. Sidney Wolfe, director of the Public Citizen's health research group, who filed a suit against use of the drug, said it was administered so sloppily that nobody knew who took it. Maj. Gen. Blanck said that there was a risk of minor side effects, but that these were worthwhile to be "prepared for exposure to deadly biological and chemical warfare agents." [7]
As reported above under Group II disorders, Brian Martin also claimed to have had side effects from the drug pyridostigmine. According to Martin, the drug made him jittery and made his vision "jiggle."
Steve Hudspeth, assigned to the 1454th Transportation Company, also reported getting very sick from the nerve agent pre-treatment pills. He reported severe nausea and diarrhea that did not abate until he stopped taking the pills after two days. He recalled thinking that "if I'm going to feel like this I might as well be dead." Mr. Hudspeth currently suffers from memory loss, fatigue, sore muscles and joints, insomnia, cough, some night sweats, diverticulitis, diarrhea, kidney stones, bloody stools, urinary urgency, growth on his eye, rashes, tingling and itching sensations, and depression and irritability. [8]
Chemically related to pesticides, nerve agents such as Sarin, Soman, Tabun, and VX kill by interfering with the metabolic processes, and cause a buildup of a chemical messenger in the human metabolic process called acetylcholine, which operates in the gap between the nerve and the muscle cells. A buildup of acetylcholine may cause drooling, excessive sweating, cramping, vomiting, confusion, irregular heart beat, convulsions, loss of consciousness and coma. [9] Little, however, is known about the consequences of non-lethal exposure to these toxins.
Nerve gas pre-treatment drugs such as pyridostigmine bromide, paradoxically, also meddle with these metabolic processes by creating carbamate-inhibited acetylcholinesterase, which interferes with the actions of nerve gas -- theorectically permitting the process to be partially reversed. [10]
An article concerning a retrospective study conducted by the military on the effects of administration of pyridostigmine bromide appeared in the August 1991 Journal of the American Medical Association. According to the article 30mg of oral pyridostigmine bromide was administered to 41,650 members of the XVIII Airborne Corps, every eight hours for 1-7 days while under threat of nerve agent attack during Operation Desert Storm. The study observed that "about half of the population that received the drug noted physiologic changes that were not incapacitating, such as increased flatus, abdominal cramps, soft stools, and urinary urgency." "Approximately 1% of the soldiers believed they had effects that warranted medical attention, but fewer than 0.1% had effects sufficient to discontinue the drug. Non-incapacitating symptoms often occurred; however, the military mission was not impaired." Other symptoms noted in the article are headaches, rhinorrhea (running nose), diaphore! sis (p erspiration), nausea, and tingling of the extremities.
The results of this study and the coincidence of symptoms with many of those now being experienced by the veterans of the Gulf War suggests that the raw data and case histories which formed the basis for this study should be made available to researchers. This data can provide valuable information to conduct a second study of the possible long term effects of the administration of this drug on otherwise healthy individuals. Further, another independent study of the additive, synergistic, or even possible potentiating effects of pyridostigmine bromide combined with organophosphate pesticides, insect repellents such as DEET, and/or trace amounts of nerve agents on key neurotransmission regulators and secondary regulators must be considered. [11]
Other Identifiable Exposures
Reported Contact with Iraqi Enemy Prisoners of War
On April 4, 1994, several members of the 371st Chemical Company, Army Reserve Center, Greenwood, South Carolina, reported to Committee staff that elements of the unit were deployed on several occasions to decontaminate buses used to transport Iraqi enemy prisoners of war (EPWs) to detention camps inside Saudi Arabia. They were never advised of the reason these decontamination missions were necessary. [12]
A number of military police and other units who guarded the EPWs had close and continuing contact with them. Many individuals in these units are now reporting very high rates of illnesses in their units to Committee staff. The symptoms these Gulf War veterans describe are consistent with those commonly associated with Gulf War Syndrome. Committee staff has also been informed that the 300th Medical Brigade was responsible for the EPW health care during and after the war. While the Committee has received anecdotal information regarding the health status of the Iraqis and their symptoms, certainly medical records were established and retained regarding their care while in Coalition custody.
Given the reported high rate of illnesses among these military police units, and the possible relationship between the illnesses being suffered by these veterans and those which were reported by the EPWs, the raw data from the medical units which treated the EPWs should be immediately released to aid independent research into the causes of these illnesses.
Chemical Agent Resistant Coating (CARC)
CARC coatings need to be resistant to chemicals that are required to decontaminate military equipment that has been exposed to chemical and/or biological warfare agents. After cleaning with these decontamination chemicals, vehicles treated with CARC can be placed back into service immediately, without stripping and repainting. There have been several generations of CARC coatings. According to published sources, the military specifications for these coatings vary with the type of equipment to be used. [13]
The first generation of CARC contained lead and hexavalent chrome. Later these items were removed and the CARC was made VOC (volatile organic compound compliant). Prior to the Gulf War, the CARC specification was for a "high solids coating without exempt solvent." [14]
Committee staff has received calls from members of several National Guard and Army Reserve Units in Florida and Michigan who were detailed to apply these coatings to U.S. military vehicles during their service in the Gulf War. According to these veterans, many members of the units are suffering from the symtoms similar to those of other affected veterans. There have also been a number of anecdotal reports received by the Committee suggesting that unprotected exposures to CARC can have neurotoxological effects similar to exposures to other neurotoxins.
According to a published report in 1993, Dr. William Johnson, formerly of the Eisenhower Army Medical Center at Fort Gordon, Georgia, noted in a report prepared for Congress, that many of these soldiers worked 12 hour days in poorly ventilated enclosures -- initially with no respirators. This report is consistent with information received by Committee staff.
While these duties were certainly necessary to perform, the failure to provide appropriate safety equipment to these individuals should be investigated further, not only for its impact on the health of the individuals but also for its impact on the ultimate readiness of these units to perform their mission. The chemical nature and the hazards associated with exposure to the various CARCs should be easily identified. Further, a study into the rates and types of illnesses being experienced by these units could be easily undertaken since the units would be readily identifiable.
Committee staff has developed no information to date that suggests these coatings represent a hazard once they are applied and cured.
Depleted Uranium Ammunition
Several different armor-penetrating munitions used during Operation Desert Storm were tipped with depleted uranium (DU) and encased in aluminum. The Persian Gulf War marked the first time such shells were used in combat. The penetrators are made of uranium rods from nuclear power plants and according to James Mathews, in an article that appeared in the Journal of the National Cancer Institute in July 1993, the uranium is depleted of the more volatile material, including the potent isotopes U-235 and U-238. [15]
According to Mathews, "When depleted-uranium penetrators strike their target, the aluminum covering is torn away and a large protion of the kinetic energy is dissipated as heat. The heat of the impact causes the depleted uranium to oxidize or burn momentarily." [16]
When uranium particles enter the body, they become lodged in bones or major organs, affecting the bone marrow and producing DNA damage. In previous congressional testimony, Mathews reports, Maj. Gen. Ronald R. Blanck, commander of Walter Reed Army Medical Center, Washington, D.C., stated that "careful analysis of [servicemen exposed to] depleted uranium suggests there will be no significant increase in risk to health, either in the short or long-term." Medical evaluations have been conducted by the Boston VA Medical Center on a number of soldiers identified as having the greatest potential for inhaling or ingesting depleted uranium dusts, mainly soldiers that prepared damaged battlefield vehicles for shipment back to the United States.
"The results of those examinations have shown no effects of uranium toxicity, and no uranium residues or byproducts were detected," said Blanck. [17]
The U.S. Armed Forces Radiological Reserach Institute is conducting a five year study into the hazards associated with U.S. military equipment and munitions that use depleted uranium. The preliminary results of that research should be made available to researchers and physicians to provide a basis for determining if exposure to unexpended or expended depleted uranium munitions is a serious health hazard.
Finally, individual dosimeters were reportedly issued to many of the soldiers who fought in the Persian Gulf War to measure radiological hazards. It has been reported to Committee staff that at least some of these dosimeters were collected from the soldiers who participated in the conflict prior to their leaving the Gulf. [18] In order to facilitate the research currently underway, and to provide information to researchers as to the level of exposure by location, the Department of Defense should release information regarding the readings from these dosimeters. If this information is not readily available, the National Institute of Standards and Technology could easily assess the level of emission related to these materials, if necessary, to provide information to both scientific and medical researchers attempting to find a cause for the illnesses being experienced to those individuals who may have been exposed to these materials. This information is also vital to ensure t! hat if a danger exists, appropriate safeguards will be taken, whenever possible, in future conflicts.
Environmental Exposures
With the initiation of the "ground war" on February 24, 1991, Iraqi forces set fire to over 600 oil wells located inside Kuwait. The contamination from these fires had a dramatic impact on the environment and the smoke was so thick that often there was darkness. In the areas where the fires were burning, Coalition soldiers were covered with an inhaled oil and soot. Even when they were able to shower, often they had no clean uniforms to replace the oil soaked ones. Other environmental hazards that have been previously considered include heater fuel fumes, pesticides, insect repellent, petrochemicals, and electromagnetic radiation from radars and communications equipment. While many researchers have discounted these exposures as causing Gulf War Syndrome since these exposures are not unique to the Gulf War environment, nevertheless, the results of the research that has been conducted in these areas by the Department of Defense and the Department of Veteran Affairs, incl! uding available data sets, case histories and diagnostic breakdown informati on, must be made available to assist medical researchers in furthering their research, and physicians in treating their patients.
Decontamination of Equipment Returned from the Persian Gulf Theater of Operations
Beginning in November 1993, Committee staff began receiving reports that a number of Department of Defense civilian personnel at the Anniston, Alabama and Sharpsite, California Army Depots were beginning to experience symptoms consistent with those of the Gulf War veterans. These individuals were assigned to clean, repair, and upgrade military vehicles and other equipment returning from the Southwest Asia theater of operations. [19]
No further information has been developed regarding these reports. Further investigation, however, appears warranted into what, if any, hazardous substances may have been transported on equipment that would cause these symptoms. This type of information may assist in narrowing the scope of the research in determining the causes of Gulf War Syndrome.
Transmission
Over the past seven months, Committee staff has interviewed in varying detail over 1,000 Gulf War veterans who claim to be suffering from many of the symptoms commonly associated with Gulf War Syndrome. As a result of these interviews, it has been learned that most of the spouses and many of the children of Gulf War veterans are suffering from many of the same symptoms. Several published reports have recently appeared that suggest that Gulf War Syndrome may be transmittable, that it may be causing miscarriages, and that it may be causing birth deficiencies and some birth defects in newborns. [20]
During a February 21, 1994 Gulf War veterans round table meeting held in Lansing, Michigan, Chairman Donald W. Riegle, Jr. met with 9 Gulf War veterans and their wives to discuss their health problems. Of the 9 Gulf War veterans present, 20 additional individuals in their immediate families who were also suffering from many of the same symptoms were also identified.
In an effort to determine the scope and nature of symptom transmission, a survey of those individuals who have contacted the Committee is currently underway. The purpose of the survey is to determine the symptoms currently being suffered by the Gulf War veterans, those being transmitted to family members, and the number and rate of birth deficiencies being experienced within this population. The final results of this survey will not be available until later this year.
The issue of the possible transmission of Gulf War Syndrome is one that recrafts the issue of national security. Surely there are some aspects of the Department of Defense's chemical and biological warfare defense programs that merit secrecy. However, when the secrecy of those programs interfere with the safety of the citizenry, then one must understand that the notion of national security rests primarily in the security of the people and not in the secrecy of vulnerability.
_______________
Notes:
1. For a detailed discussion of the investigation into the adverse effects of these drugs see Preliminary Staff Findings: Is Military Research Hazardous to Veterans' Health? Lessons from the Persian Gulf U.S. Senate Committee on Veterans' Affairs staff report to Chairman Jay Rockefeller (May 6, 1994).
2. Patrick Cockburn, "Gulf War Guinea Pigs Tell Senate of Mystery Illness; Experts Point to Experimental Drugs Given to Troops in Case of Gas Attack," The Independent (July 2, 1993), 13; Brian Christie, "Viewers Question Experts About Vets with Gulf War Illness," Cable News Network Transcript #267-2 (June 10, 1993).
3. Staff interview with General Blanck.
4. Committee staff interviews with the Michigan Department of Public Health.
5. Dr. Edward Martin, Principal Assistant Secretary of Defense for Health Affairs (Acting), "Military Use of Investigational Medical Products," Statement before the Senate Committee of Veterans' Affairs (May 06, 1994).
6. Patrick Cockburn, "Gulf War Guinea Pigs Tell Senate of Mystery Illness; Experts Point to Experimental Drugs Given to Troops in Case of Gas Attack," The Independent (July 2, 1993), 13.
7. Ibid.
8. Staff Interviews.
9. William Booth, "Gas Masks, Antidote Cause Three Deaths and Illness in Israel," Washington Post (January 19, 1991) A20.
10. Col. Michael A Dunn, MC, USA, and Frederick R. Sidell, "Progress in Medical Defense Against Nerve Agents," Journal of the American Medical Association (August 4, 1989), 649-652.
11. Banking Committee staff interview with Dr. James Moss, U.S. Department of Agriculture, March 1994. See also Preliminary Staff Findings: Is Military Research Hazardous to Veterans' Health? Lessons from the Persian Gulf. U.S. Senate Committee on Veterans' Affairs staff report to Chairman Jay Rockefeller (May 6, 1994).
12. Staff interviews.
13. Joe Schrantz, "Excitement Stirs in Aerospace/Military Coatings," Industrial Finishings, Vol. 65, No. 9 (September 1989), 18.
14. Ibid.
15. James Mathews, "Radioactive Bullets Raise Cancer Fears, Journal of the National Cancer Institute. Vol. 85 (July 7, 1993), 1029-1030.
16. Ibid.
17. Ibid.
18. Staff interviews.
19. Staff interviews.
20. Ron Martz, "Mississippi Vets Blame Gulf War for Sick Kids," The Atlanta Journal and Constitution (January 22, 1994), A5; Simon Tisdale, "Gulf Babies Maimed at Birth," The Guardian (December 23. 1993), 1, Ed Timms and Steve McGonigle, "Gulf Unit Cites Babies' Illnesses at Meeting," The Dallas Morning News (November 23, 1993), 4 A; Ed Timms, "Some Active Duty Troops are Suffering in Silence," The Dallas Morning News (November 14. 1993), 15A, Richard Serrano. "Pentagon Feels Heat Over Gulf War Disease," Chicago Sun Times (November 7, 1993), 28.
United States Dual-Use Exports to Iraq and Their Impact
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Chapter 4, Part 2: Conclusions
Chemical/Biological Warfare Agent Exposure: Why Wasn't Everyone Affected?
The ability of someone to resist an illness, disease, or the adverse effects of a medication varies with each individual. Not everyone who received nerve agent pre-treatment drugs exhibited adverse effects. According to the Centers for Disease Control not everyone who is exposed to nerve gas will cross a toxic threshold at the same time. Certainly, there is a threshold beyond which such exposure will surely be lethal. This is what has come to be accepted as the effect of nerve gas exposure.
The results of this investigation suggest that there is, in fact, a relationship between dosage and harmful effects. A number of units who believe they suffered a direct chemical weapons attack report illness rates over 50%. The Czech chemical decontamination unit, which suffered only indirect exposure and might be expected to be well prepared against chemical exposure, reports an illness rate of 10%. The extent of exposure in the larger population in the Gulf at the time, and the rate of illnesses, is unknown. The number of Gulf War veterans who have signed up for the Persian Gulf Registry examination is now over 17,000.
Nerve agents like Sarin kill by disrupting the metabolic processes, causing a buildup of a chemical messenger (acetylcholine) by inhibiting the production of acetylcholinesterase, a key regulator of neurotransmission. Nerve agent pre-treatment drugs (NAPP) administered to U.S. servicemen and women, such as pyridostigmine bromide, also disrupt these metabolic processes by creating a carbamate-inhibited acetylcholinesterase, which preempts the action of the nerve agent. Several veterans suffering from Gulf War illnesses have testified before House and Senate Veterans Affairs Committee and believe that these illnesses are related to the permanent adverse side effects from this drug. Further, the efficacy of the biological warfare defense inoculations merits further research.
Chemical/Biological Warfare Agent Exposure: Did the Military Know or Suspect that Individuals were Exposed to these Hazardous Substances?
The evidence cited above and the statements of the witnesses will have to be evaluated on their own merits in this regard. During the course of this investigation, a medical questionnaire was received from one of the veterans currently suffering from Gulf War illnesses. This questionnaire like the other evidence and statements must be weighed on its own merits. The following information is solicited on this document, an overprint to SF600:
1. What diseases or injuries did you have in the Southwest Asia region?
2. Are you receiving any medicine, or other treatment, at the present time?
3. Do you have fever, fatigue, weight loss, or yellow jaundice?
4. Do you have any swelling of lymph nodes, stomach, or other body parts?
5. Do you have any rash, skin infection, or sores?
6. Do you have a cough or sinus infection?
7. Do you have stomach or belly pain, nausea, diarrhea, or bloody bowel movements?
8. Do you have urinary problems such as blood or stones in urine or pain and burning with urination?
9. Have you had nightmares or trouble sleeping?
10. Have you had recurring thoughts about your experiences during Desert Shield/Desert Storm?
11. Do you have any reason to believe that you, or any members of your unit, were exposed to chemical warfare or germ warfare?
Forms such as this suggest that the military expected, for whatever reason, to see symptomologies such as those that are currently being experienced. This information, as well as the information maintained in the medical records of U.S. forces and the Iraqi EPWs may provide information that will assist medical researchers in determining causal links. This issue should be further investigated.
The Need for Immediate Primary Scientific Research and Advanced Medical Research
Thousands of veterans of the Gulf War are reporting symptoms of memory loss, muscle and joint pain, intestinal and heart problems, fatigue, rashes, sores, and running noses. A number of veterans who have exhibited these symptoms since returning from the Gulf War have subsequently died. Physicians have been unable to diagnose the cause of the disorders.
The following symptoms have been identified as those most commonly reported by veterans:
• recurring severe headaches
• fatigue
• joint and muscle pain (particularly in knees, ankles, shoulders, and back)
• memory loss (often described as an inability to concentrate)
• recurring rashes (sometimes severe and often causing skin discoloration or described as mosquito bite-like or small with water pustules)
• lumps at joint areas
• lumps under skin
Symptoms most commonly reported by veterans (cont.):
• depression, irritability
• night sweats
• insomnia
• urinary urgency and frequency
• diarrhea (sometimes bloody) or constipation
• gastrointestinal problems (mausea, swollen stomach, gas)
• dizziness or blackouts
• blurry vision
• photosensitivity (excessive sensitivity to bright lights)
• shortness of breath
• coughing
• abnormal hair loss
• bleeding gums (or other serious dental problems)
• swollen lymph nodes
• sinus infections
• chest pains
female veterans only:
• chronic or recurring vaginal yeast infections
• menstrual irregularities
• excessive bleeding and severe cramping
Little is known about the long-term consequences of exposure to low levels of nerve gas, and even less about complications which might arise from using combined agent weapons. Further, little is known about other difficulties associated with interfering with the neurotransmission process. Non-lethal exposure to pesticides, however, has manifested itself in memory loss. Nearly every bodily process requires a properly functioning nervous system to operate.
The following is a summary, not offered as diagnostic evidence, suggesting how some of the symptoms noted could be rooted in neurotransmission related disorders:
Memory Loss: Although neuroscience is a long way from explaining the memory functions of the human brain, considerable strides have been made towards understanding how neurons are modified by experience and how those modifications are maintained for extended periods of time. The ability to remember is regulated, however, by neural processing. [21] On August 25, 1993, Dr. Howard Hu, a researcher with Physicians for Human Rights who participated in the investigation of the use of nerve gas by the Iraqi government against the Kurds, suggested that the effects of non-lethal exposures to nerve agents could be similar to those involving non-lethal exposures to pesticides. Dr. Hu said these disorders are generally neuropsychological and include memory loss. [22]
Muscle Pains: Myasthenia Gravis is a disease causing progressive muscle weakness. It has been shown that the disease is an autoimmune reaction to the acetylcholine-gated channels in the neuromuscular junction. According to Lloyd D. Partridge and L. Donald Partridge, many drugs and toxins, including pesticides and nerve gas, are known to exhibit their effects through specific actions at the neuromuscular junctions, blocking the action of acetylcholinesterase. [23]
Joint Pains: When the force generated by a muscle acts on a load, there is a requisite exchange of energy between the muscle and the load. A failure of the nervous system to send impulses to effector muscles can result in the failure of effector muscles to provide the resistance necessary to protect joints from excessive torque. This failure, and the resultant joint pain, is consistent with the action of any agent or medication which functions by disrupting the communication process operating in the gap between the nerve and the muscle cells. [24]
Gastrointestinal Disorders: As a combined neural operation, the neural signals that control digestive functions, such as in the complex nervous system of the gut, are largely, but not entirely, independent of the central nervous system (CNS). Many of the control functions are conducted by local nerve networks and the endocrine systems. These digestive functions, however, depend on the ability of the CNS and local nerve networks to function properly. [25]
Heart problems, running noses and virtually every other problem lumped under the heading of Gulf War Illnesses can be explained by neurophysical and neuropsychiatric disorders. Some of the non-chemical warfare related diseases involving a disruption in the acetylcholine-gated channels in the neuromuscular messenger junctions, such as myasthenia gravis, while treatable, are irreversible. Neurotransmission disorders resulting from disrupted physiological processes, such as those regulating acetylcholines (including toxin acetylcholine and acetylcholinesterase) may be contributing to the symptomologies observed. Detection of these types of disorders may only be possible using highly sophisticated, computer-read electroencephalograms (EEG). Further, given the possibility that some of these individuals were exposed to biotoxins and other biological agents, scientists and physicians will need to use sophisticated procedures including DNA plasmid screening, bacteriological! screening, mycological screening, viral screening, and toxicological screening.
Conclusions
Thousands of American servicemen and women are reportedly suffering from memory loss, muscle and joint pain, intestinal and heart problems, fatigue, rashes, sores, and running noses as a result of their service in the Gulf War. A number of veterans who have exhibited these symptoms since returning from the Gulf War reportedly have died. Members of their immediate families are now beginning to contract some of the illnesses. Physicians have been unable to diagnose or treat the cause of the disorders.
Despite the Department of Defense's position that no evidence exists for exposure to chemical warfare agents during the Gulf War, this investigation is establishing that there is substantial evidence supporting claims that U.S. servicemen and women were exposed to low level chemical warfare agents and possibly biological agents and toxins from a variety of sources. This exposure may account for many of the Gulf War Illness symptoms. Little is known about the long term consequences of exposure to low levels of nerve gas, although most are known to have cumulative toxic effects.
Even less is known about complications which might arise from exposure to combined agents and combined agent weapons. The combined agent strategy is intended to frustrate efforts at diagnosing these illnesses. Non-lethal exposure to pesticides can result in memory loss, and nerve agents are chemically related to pesticides. Many of the veterans complaining of Gulf War Syndrome illnesses suffer from, among other disorders, memory loss. Many of the identified chemical and biological agents interfere with the body's neurotransmission processes, effecting the regulation of acetylcholine, neurotoxin acetylcholine, and other necessary enzymes required by nearly every bodily process. In order to detect irregularities such as those which might be caused by exposure to nerve gas, computer read electroencephalograms are needed; a physician probably would not be able to recognize the abnormalities during a visual EEG interpretation.
If biotoxins or biological agents were used or released in the Gulf War, detection requires that physicians and scientists have some idea of what they are looking for. Further, if mycotoxins or viruses were used or released, they would be difficult to detect without the aid or advanced laboratory screen methods.
Non-lethal exposure to chemical warfare agents, some biological agents, mixed chemical/biotoxin agents and/or the administration of nerve agent pre-treatment drugs could explain many of the symptoms of the Gulf War illness, as well as the inability to diagnose the disorders. Other possible causes for Gulf War syndrome have been suggested, such as exposure to pesticides, petrochemicals, burning landfills and oil wells, depleted uranium from anti-tank munitions, or exposure to other environmental hazards. Many of these possibilities already have been investigated and discounted. Additionally, these types of exposures are not specific to the Middle East or to the Gulf War and the evidence for these hazards causing the large number of unexplained illnesses is less than compelling. Each of these possible causes of unexplained illnesses, however, should be systematically researched.
_______________
Notes:
21. Lloyd D. Partridge and L Donald Partridge, The Nervous System: Its Function and Interaction with the World (Cambridge, Massachusetts MIT Press, 1993).
22. Interview with Dr. Howard Hu, Physicians for Human Rights on August 25, 1993.
23. Lloyd D. Partridge and L. Donald Partridge, The Nervous System: Its Function and Interaction with the World (Cambridge, Massachusetts: MIT Press, 1993)
24. Ibid.
25. Ibid.
Chemical/Biological Warfare Agent Exposure: Why Wasn't Everyone Affected?
The ability of someone to resist an illness, disease, or the adverse effects of a medication varies with each individual. Not everyone who received nerve agent pre-treatment drugs exhibited adverse effects. According to the Centers for Disease Control not everyone who is exposed to nerve gas will cross a toxic threshold at the same time. Certainly, there is a threshold beyond which such exposure will surely be lethal. This is what has come to be accepted as the effect of nerve gas exposure.
The results of this investigation suggest that there is, in fact, a relationship between dosage and harmful effects. A number of units who believe they suffered a direct chemical weapons attack report illness rates over 50%. The Czech chemical decontamination unit, which suffered only indirect exposure and might be expected to be well prepared against chemical exposure, reports an illness rate of 10%. The extent of exposure in the larger population in the Gulf at the time, and the rate of illnesses, is unknown. The number of Gulf War veterans who have signed up for the Persian Gulf Registry examination is now over 17,000.
Nerve agents like Sarin kill by disrupting the metabolic processes, causing a buildup of a chemical messenger (acetylcholine) by inhibiting the production of acetylcholinesterase, a key regulator of neurotransmission. Nerve agent pre-treatment drugs (NAPP) administered to U.S. servicemen and women, such as pyridostigmine bromide, also disrupt these metabolic processes by creating a carbamate-inhibited acetylcholinesterase, which preempts the action of the nerve agent. Several veterans suffering from Gulf War illnesses have testified before House and Senate Veterans Affairs Committee and believe that these illnesses are related to the permanent adverse side effects from this drug. Further, the efficacy of the biological warfare defense inoculations merits further research.
Chemical/Biological Warfare Agent Exposure: Did the Military Know or Suspect that Individuals were Exposed to these Hazardous Substances?
The evidence cited above and the statements of the witnesses will have to be evaluated on their own merits in this regard. During the course of this investigation, a medical questionnaire was received from one of the veterans currently suffering from Gulf War illnesses. This questionnaire like the other evidence and statements must be weighed on its own merits. The following information is solicited on this document, an overprint to SF600:
1. What diseases or injuries did you have in the Southwest Asia region?
2. Are you receiving any medicine, or other treatment, at the present time?
3. Do you have fever, fatigue, weight loss, or yellow jaundice?
4. Do you have any swelling of lymph nodes, stomach, or other body parts?
5. Do you have any rash, skin infection, or sores?
6. Do you have a cough or sinus infection?
7. Do you have stomach or belly pain, nausea, diarrhea, or bloody bowel movements?
8. Do you have urinary problems such as blood or stones in urine or pain and burning with urination?
9. Have you had nightmares or trouble sleeping?
10. Have you had recurring thoughts about your experiences during Desert Shield/Desert Storm?
11. Do you have any reason to believe that you, or any members of your unit, were exposed to chemical warfare or germ warfare?
Forms such as this suggest that the military expected, for whatever reason, to see symptomologies such as those that are currently being experienced. This information, as well as the information maintained in the medical records of U.S. forces and the Iraqi EPWs may provide information that will assist medical researchers in determining causal links. This issue should be further investigated.
The Need for Immediate Primary Scientific Research and Advanced Medical Research
Thousands of veterans of the Gulf War are reporting symptoms of memory loss, muscle and joint pain, intestinal and heart problems, fatigue, rashes, sores, and running noses. A number of veterans who have exhibited these symptoms since returning from the Gulf War have subsequently died. Physicians have been unable to diagnose the cause of the disorders.
The following symptoms have been identified as those most commonly reported by veterans:
• recurring severe headaches
• fatigue
• joint and muscle pain (particularly in knees, ankles, shoulders, and back)
• memory loss (often described as an inability to concentrate)
• recurring rashes (sometimes severe and often causing skin discoloration or described as mosquito bite-like or small with water pustules)
• lumps at joint areas
• lumps under skin
Symptoms most commonly reported by veterans (cont.):
• depression, irritability
• night sweats
• insomnia
• urinary urgency and frequency
• diarrhea (sometimes bloody) or constipation
• gastrointestinal problems (mausea, swollen stomach, gas)
• dizziness or blackouts
• blurry vision
• photosensitivity (excessive sensitivity to bright lights)
• shortness of breath
• coughing
• abnormal hair loss
• bleeding gums (or other serious dental problems)
• swollen lymph nodes
• sinus infections
• chest pains
female veterans only:
• chronic or recurring vaginal yeast infections
• menstrual irregularities
• excessive bleeding and severe cramping
Little is known about the long-term consequences of exposure to low levels of nerve gas, and even less about complications which might arise from using combined agent weapons. Further, little is known about other difficulties associated with interfering with the neurotransmission process. Non-lethal exposure to pesticides, however, has manifested itself in memory loss. Nearly every bodily process requires a properly functioning nervous system to operate.
The following is a summary, not offered as diagnostic evidence, suggesting how some of the symptoms noted could be rooted in neurotransmission related disorders:
Memory Loss: Although neuroscience is a long way from explaining the memory functions of the human brain, considerable strides have been made towards understanding how neurons are modified by experience and how those modifications are maintained for extended periods of time. The ability to remember is regulated, however, by neural processing. [21] On August 25, 1993, Dr. Howard Hu, a researcher with Physicians for Human Rights who participated in the investigation of the use of nerve gas by the Iraqi government against the Kurds, suggested that the effects of non-lethal exposures to nerve agents could be similar to those involving non-lethal exposures to pesticides. Dr. Hu said these disorders are generally neuropsychological and include memory loss. [22]
Muscle Pains: Myasthenia Gravis is a disease causing progressive muscle weakness. It has been shown that the disease is an autoimmune reaction to the acetylcholine-gated channels in the neuromuscular junction. According to Lloyd D. Partridge and L. Donald Partridge, many drugs and toxins, including pesticides and nerve gas, are known to exhibit their effects through specific actions at the neuromuscular junctions, blocking the action of acetylcholinesterase. [23]
Joint Pains: When the force generated by a muscle acts on a load, there is a requisite exchange of energy between the muscle and the load. A failure of the nervous system to send impulses to effector muscles can result in the failure of effector muscles to provide the resistance necessary to protect joints from excessive torque. This failure, and the resultant joint pain, is consistent with the action of any agent or medication which functions by disrupting the communication process operating in the gap between the nerve and the muscle cells. [24]
Gastrointestinal Disorders: As a combined neural operation, the neural signals that control digestive functions, such as in the complex nervous system of the gut, are largely, but not entirely, independent of the central nervous system (CNS). Many of the control functions are conducted by local nerve networks and the endocrine systems. These digestive functions, however, depend on the ability of the CNS and local nerve networks to function properly. [25]
Heart problems, running noses and virtually every other problem lumped under the heading of Gulf War Illnesses can be explained by neurophysical and neuropsychiatric disorders. Some of the non-chemical warfare related diseases involving a disruption in the acetylcholine-gated channels in the neuromuscular messenger junctions, such as myasthenia gravis, while treatable, are irreversible. Neurotransmission disorders resulting from disrupted physiological processes, such as those regulating acetylcholines (including toxin acetylcholine and acetylcholinesterase) may be contributing to the symptomologies observed. Detection of these types of disorders may only be possible using highly sophisticated, computer-read electroencephalograms (EEG). Further, given the possibility that some of these individuals were exposed to biotoxins and other biological agents, scientists and physicians will need to use sophisticated procedures including DNA plasmid screening, bacteriological! screening, mycological screening, viral screening, and toxicological screening.
Conclusions
Thousands of American servicemen and women are reportedly suffering from memory loss, muscle and joint pain, intestinal and heart problems, fatigue, rashes, sores, and running noses as a result of their service in the Gulf War. A number of veterans who have exhibited these symptoms since returning from the Gulf War reportedly have died. Members of their immediate families are now beginning to contract some of the illnesses. Physicians have been unable to diagnose or treat the cause of the disorders.
Despite the Department of Defense's position that no evidence exists for exposure to chemical warfare agents during the Gulf War, this investigation is establishing that there is substantial evidence supporting claims that U.S. servicemen and women were exposed to low level chemical warfare agents and possibly biological agents and toxins from a variety of sources. This exposure may account for many of the Gulf War Illness symptoms. Little is known about the long term consequences of exposure to low levels of nerve gas, although most are known to have cumulative toxic effects.
Even less is known about complications which might arise from exposure to combined agents and combined agent weapons. The combined agent strategy is intended to frustrate efforts at diagnosing these illnesses. Non-lethal exposure to pesticides can result in memory loss, and nerve agents are chemically related to pesticides. Many of the veterans complaining of Gulf War Syndrome illnesses suffer from, among other disorders, memory loss. Many of the identified chemical and biological agents interfere with the body's neurotransmission processes, effecting the regulation of acetylcholine, neurotoxin acetylcholine, and other necessary enzymes required by nearly every bodily process. In order to detect irregularities such as those which might be caused by exposure to nerve gas, computer read electroencephalograms are needed; a physician probably would not be able to recognize the abnormalities during a visual EEG interpretation.
If biotoxins or biological agents were used or released in the Gulf War, detection requires that physicians and scientists have some idea of what they are looking for. Further, if mycotoxins or viruses were used or released, they would be difficult to detect without the aid or advanced laboratory screen methods.
Non-lethal exposure to chemical warfare agents, some biological agents, mixed chemical/biotoxin agents and/or the administration of nerve agent pre-treatment drugs could explain many of the symptoms of the Gulf War illness, as well as the inability to diagnose the disorders. Other possible causes for Gulf War syndrome have been suggested, such as exposure to pesticides, petrochemicals, burning landfills and oil wells, depleted uranium from anti-tank munitions, or exposure to other environmental hazards. Many of these possibilities already have been investigated and discounted. Additionally, these types of exposures are not specific to the Middle East or to the Gulf War and the evidence for these hazards causing the large number of unexplained illnesses is less than compelling. Each of these possible causes of unexplained illnesses, however, should be systematically researched.
_______________
Notes:
21. Lloyd D. Partridge and L Donald Partridge, The Nervous System: Its Function and Interaction with the World (Cambridge, Massachusetts MIT Press, 1993).
22. Interview with Dr. Howard Hu, Physicians for Human Rights on August 25, 1993.
23. Lloyd D. Partridge and L. Donald Partridge, The Nervous System: Its Function and Interaction with the World (Cambridge, Massachusetts: MIT Press, 1993)
24. Ibid.
25. Ibid.
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Re: United States Dual-Use Exports to Iraq and Their Impact
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Appendix A - Material Safety Data Sheets
Chemical Nerve Agents
Tabun (GA)
Sarin (GB)
Soman (GD)
VX
Blister Agents
Sulfur Mustard (HD), (HDT)
Sulfur Mustard (HT)
[PAGES 389-433 OMITTED HERE]
Chemical Nerve Agents
Tabun (GA)
Sarin (GB)
Soman (GD)
VX
Blister Agents
Sulfur Mustard (HD), (HDT)
Sulfur Mustard (HT)
[PAGES 389-433 OMITTED HERE]
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Material Safety Data Sheet -- Lethal Nerve Agent Tabun (GA)
Section I: General Information
MANUFACTURER'S NAME: Department of the Army
MANUFACTURER'S ADDRESS:
U.S. Army Armament, Munitions and Chemical Command
Chemical Research, Development and Engineering Center
ATTN: SMCCR-CMS-E
Aberdeen Proving Ground, MD 21010-5423
CAS REGISTRY NUMBER: None
CHEMICAL NAME: Ethyl N,N-dimethylphosphoramidocyanidate
TRADE NAME AND SYNONYMS:
• Ethyl dimethylplosphoramidocyanidate
• Dimethylaminoethoxy-cyanophosphine oxide
• Dimethylamidoethoxyphosphoryl cyanide
• Ethyldimethylaminocyanophosphonate
• Ethyl ester of dimethylphosphoroamidocyanidic acid
• Ethyl phosphorodimethylamidocyanidate
• GA
• EA1205
• Tabun
CHEMICAL FAMILY: Organophosphorous compound
FORMULA: C5 H11 N2 02 P
NFPA 704 SIGNAL:
• Health - 4
• Flammability - 2
• Reactivity - 1
Section II: Composition
INGREDIENTS FORMULA PERCENTAGE AIRBORNE
NAME BY WEIGHT EXPOSURE LIMIT (AEL)
GA C5 H11 N2 02 P 100 0.0001 mg/m3
Return to Top of Page
Section III: Physical Data
BOILING POINT DEG F (DEG C): 247.5 DEG C
VAPOR PRESSURE (mm hg): 0.07 @ 24 DEG C
VAPOR DENSITY (AIR=1): 5.6
SOLUBILITY IN WATER (g/100 g): 9.8 @ 25 DEG C/ 7.2 @ 20 DEG C
SPECIFIC GRAVITY (H20=1): Not available
FREEZING (MELTING) POINT: -50 DEG C
AUTOIGNITION TEMPERATURE DEG F (DEG C): Not available
VISCOSITY (CENTISTOKES): 2.18 @ 25 DEG C
PERCENTAGE VOLATILE BY VOLUME: 610 mg/m3 @ 25 DEG C
EVAPORATION RATE: Not available
APPEARANCE AND ODOR: Colorless to brown liquid. Faintly fruity; none when pure
Section IV: Fire and Explosion Data
FLASHPOINT: 78 DEG C
FLAMMABILITY LIMITS (% by volume): Not available
EXTINGUISING MEDIA: Water, fog, foam, CO2 - Avoid using extinguishing methods that will cause splashing or spreading of the GA.
UNUSUAL FIRE & EXPLOSION HAZARDS: Fires involving this chemical may result in the formation of hydrogen cyanide.
SPECIAL FIRE FIGHTING PROCEDURES:
All persons not engaged in extinguishing the fire should be immediately evacuated from the area. Fires involving GA should be contained to prevent contamination to uncontrolled areas. When responding to a fire alarm in buildings or areas containing agents, firefighting personnel should wear full firefighter protective clothing (without TAP clothing) during chemical agent firefighting and fire rescue operations.
Respiratory protection is required. Positive pressure, full facepiece, NIOSH-approved self- contained breathing apparatus (SCBA) will be worn where there is danger of oxygen deficiency and when directed by the fire chief or chemical accident/incident (CAI) operations officer. The M9 or M17 series mask may be worn in lieu of SCBA when there is no danger of oxygen deficiency. In cases where firefighters are responding to a chemical accident/incident for rescue/reconnaissance purposes vice firefighting, they will wear appropriate levels of protective clothing (see Section 8).
Section V: Health Hazard Data
AIRBORNE EXPOSURE LIMIT (AEL): The suggested permissible airborne exposure concentration for GA for an 8-hour workday or a 40 hour work week is an 8 hour time weight average (TWA) of 0.0001 mg/m3 (2 x 10-5 ppm). This value is based on the TWA of GA as proposed in the USaEHA Technical Guide 169, "Occupational Health Guildelines for the Evaluation and Control of Occupational Exposure to Nerve Agents, GA, GB, GD, and VX." To date, however, the Occupational Safety and Health Administration (OSHA) has not promulgated a permissible exposure concentration for GA.
EFFECTS OF OVEREXPOSURE:
GA is an anticholinesterase agent similar in action to GB. Although only about half as toxic as GB by inhalation, GA in low concentrations is more irritating to the eyes than GB.
The number and severity of symptoms which appear are dependent on the quantity, and rate of entry of the nerve agent which is introduced into the body. (Very small skin dosages sometimes cause local sweating and tremors with few other effects.)
Individuals poisoned by GA display apaproximately the same sequence of symptoms regardless of the route by which the poison enters the body (whether by inhalation, absorption, or ingestion). These symptoms, in normal order of appearance, runny nose; tightness of chest; dimness of vision and pin pointing of the eye pupils; difficulty in breathing; drooling and excessive sweating; nausea; vomiting, cramps, and involuntary defecation and urination; twitching, jerking, and staggering; and headaches, confusion, drowsiness, coma, and convulsion. These symptoms are followed by cessation of breathing and death.
Onset Time of Symptoms: Symptoms appear much more slowly from skin dosage than from respiratory dosage. Although skin absorption great enough to cause death may occur in 1 to 2 minutes, death may be delayed for 1 to 2 hours. Respiratory lethal dosages kill in 1 to 10 minutes, and liquid in the eye kills almost as rapidly.
Median Lethal Dosage, Animals: LD50 (monkey, percutaneous) = 9.3 mg/kg (shaved skin); LCt50 (monkey, inhalation) = 187 mg-min/m3 (t = 10)
Median Lethal Dosage, Man: LCt50 (man, inhalation) = 135 mg-min/m3 (t = 0.5-2 min) at RMV (Respiratory Minute Volume) of 15 1/min; 200 mg-min/m3 at RMV* of 10 1/min
GA is not listed by the International Agency for Research on Cancer (IARC), American Conference of Governmental Industrial Hygienists (ACGIH). Occupational Safety and Health Administration (OSHA), or National Toxicology Program (NTP) as a carcinogen.
EMERGENCY AND FIRST AID PROCEDURES:
• INHALATION: Hold breath until respiratory protective mask is donned. If severe signs of agent exposure appear (chest tightens, pupil construction, incoordination, etc.), immediately administer, in rapid succession, all three Nerve Agent Antidote Kit(s), Mark I injectors (or atropine if directed by the local physician). Injections using the Mark I kit injectors may be repeated at 5 to 20 minute intervals if signs and symptoms are progressing until three series of injections have been administered. No more injections will be given unless directed by medical personnel. In addition, a record will be maintained of all injections given. If breathing has stopped, give artificial respiration. Mouth-to-mouth resuscitation should be used when approved mask-bag or oxygen delivery systems are not available. Do not use mouth-to-mouth resuscitation when facial contamination exists. If breathing is difficult, administer oxygen. Seek medical attention IMMEDIATELY.
• EYE CONTACT: IMMEDIATELY flush eyes with water for 10-15 minutes then don respiratory protective mask. Although miosis (pinpointing of the pupils) may be an early sign of agent exposure, an injection will not be administered when miosis is the only sign present. Instead, the individual will be taken immediately to the medical treatment facility for observation.
• SKIN CONTACT: Don respiratory protection mask and remove contaminated clothing. Immediately wash contaminated skin with copious amounts of soap and water, 10% sodium carbonate solution, or 5% liquid household bleach. Rinse well with water to remove decontaminate. Administer an intramuscular injection with the MARK I kit injectors only if local sweating and muscular twitching symptoms are observed. Seek medical attention IMMEDIATELY.
• INGESTION: Do not induce vomiting. First symptoms are likely to be gastrointestinal. IMMEDIATELY administer 2 mg. intramuscular injection of the MARK I kit auto-injectors. Seek medical attention IMMEDIATELY.
Section VI: Reactivity Data
STABILITY: Stable
INCOMPATIBILITY: Not available
HAZARDOUS DECOMPOSITION: Decomposes within 6 months at 60 DEG C. Complete decomposition in 3-1/4 hours at 150 DEG C. May produce HCN. Oxides of nitrogen, oxides of phosphorus, carbon monoxide, and hydogen cyanide.
HAZARDOUS POLYMERIZATON: Not available
Section VII: Spill, Leak and Disposal Procedures
STEPS TO BE TAKEN IN CASE MATERIAL IS RELEASED OR SPILLED: If leaks or spills occur, only personnel in full protective clothing (see section 8) will remain in area. In case of personnel contamination see section V "Emergency and First Aid Instructions."
RECOMMENDED FIELD PROCEDURES:
Spills must be contained by covering with vermiculite, diatomaceious earth, clay, fine sand, sponges, and paper or cloth towels. This containment is followed by treatment with copious amounts of aqueous Sodium Hydroxide solution (a minimum 10 wt percent). Scoop up all material and place in a fully removable head drum with a high density polyethylene liner. The decontamination solution must be treated with excess bleach to destroy the CN formed during hydrolysis. Cover the contents with additional bleach before affixing the drum head. After sealing the head, the exterior of the drum shall be decontaminated and then labeled IAW EPA and DOT regulations.
All leaking containers shall be overpacked with vermiculite placed between the interior and exterior containers. Decontaminate and label IAW EPA and DOT regulations. Dispose of the material IAW waste disposal methods provided below. Conduct general area monitoring with an approved monitor (see Section 8) to confirm that the atmospheric concentrations do not exceed the airborne exposure limit (see Sections 2 and 8).
If 10 wt percent Sodium Hydroxide is not available then the following decontaminants may be used instead and are listed in order of preference: Decontamination Solution No. 2 (DS2), Sodium Carbonate and Supertropical Bleach Slurry (STB).
RECOMMENDED LABORATORY PROCEDURES:
A minimum of 56 grams of decon solution is required for each gram of GA. The decontamination solution is agitated while GA is added and the agitation is maintained for at least one hour. The resulting solution is allowed to react for 24 hours. At the end of 24 hours, the solution must be tritrated to a pH between 10 and 12. After completion of the 24 hour period, the decontamination solution must be treated with excess bleach (2.5 mole OC1-/mole GA) to destroy the CN formed during hydrolysis.
Scoop up all material and place in a fully removable head drum with a high density polyethylene liner. Cover the contents with additional bleach before affixing the drum head. All contaminated clothing will be placed in a fully removable head drum with a high density polyethylene liner. Cover the contents of the drum with decontaminating solution as above before affixing the drum head. After sealing the head, the exterior of the drum shall be decontaminated and then labeled IAW state, EPA and DOT regulations.
All leaking containers shall be overpacked with vermiculite placed between the interior and exterior containers. Decontaminate and label IAW State, EPA and DOT regulations. Conduct general area monitoring with an approved monitor (see Section 8) to confirm that the atmospheric concentrations do not exceed the airborne exposure limit (see Sections 2 and 8).
WASTE DISPOSAL METHOD: Open pit burning or burying of GA or items containing GA.
Section I: General Information
MANUFACTURER'S NAME: Department of the Army
MANUFACTURER'S ADDRESS:
U.S. Army Armament, Munitions and Chemical Command
Chemical Research, Development and Engineering Center
ATTN: SMCCR-CMS-E
Aberdeen Proving Ground, MD 21010-5423
CAS REGISTRY NUMBER: None
CHEMICAL NAME: Ethyl N,N-dimethylphosphoramidocyanidate
TRADE NAME AND SYNONYMS:
• Ethyl dimethylplosphoramidocyanidate
• Dimethylaminoethoxy-cyanophosphine oxide
• Dimethylamidoethoxyphosphoryl cyanide
• Ethyldimethylaminocyanophosphonate
• Ethyl ester of dimethylphosphoroamidocyanidic acid
• Ethyl phosphorodimethylamidocyanidate
• GA
• EA1205
• Tabun
CHEMICAL FAMILY: Organophosphorous compound
FORMULA: C5 H11 N2 02 P
NFPA 704 SIGNAL:
• Health - 4
• Flammability - 2
• Reactivity - 1
Section II: Composition
INGREDIENTS FORMULA PERCENTAGE AIRBORNE
NAME BY WEIGHT EXPOSURE LIMIT (AEL)
GA C5 H11 N2 02 P 100 0.0001 mg/m3
Return to Top of Page
Section III: Physical Data
BOILING POINT DEG F (DEG C): 247.5 DEG C
VAPOR PRESSURE (mm hg): 0.07 @ 24 DEG C
VAPOR DENSITY (AIR=1): 5.6
SOLUBILITY IN WATER (g/100 g): 9.8 @ 25 DEG C/ 7.2 @ 20 DEG C
SPECIFIC GRAVITY (H20=1): Not available
FREEZING (MELTING) POINT: -50 DEG C
AUTOIGNITION TEMPERATURE DEG F (DEG C): Not available
VISCOSITY (CENTISTOKES): 2.18 @ 25 DEG C
PERCENTAGE VOLATILE BY VOLUME: 610 mg/m3 @ 25 DEG C
EVAPORATION RATE: Not available
APPEARANCE AND ODOR: Colorless to brown liquid. Faintly fruity; none when pure
Section IV: Fire and Explosion Data
FLASHPOINT: 78 DEG C
FLAMMABILITY LIMITS (% by volume): Not available
EXTINGUISING MEDIA: Water, fog, foam, CO2 - Avoid using extinguishing methods that will cause splashing or spreading of the GA.
UNUSUAL FIRE & EXPLOSION HAZARDS: Fires involving this chemical may result in the formation of hydrogen cyanide.
SPECIAL FIRE FIGHTING PROCEDURES:
All persons not engaged in extinguishing the fire should be immediately evacuated from the area. Fires involving GA should be contained to prevent contamination to uncontrolled areas. When responding to a fire alarm in buildings or areas containing agents, firefighting personnel should wear full firefighter protective clothing (without TAP clothing) during chemical agent firefighting and fire rescue operations.
Respiratory protection is required. Positive pressure, full facepiece, NIOSH-approved self- contained breathing apparatus (SCBA) will be worn where there is danger of oxygen deficiency and when directed by the fire chief or chemical accident/incident (CAI) operations officer. The M9 or M17 series mask may be worn in lieu of SCBA when there is no danger of oxygen deficiency. In cases where firefighters are responding to a chemical accident/incident for rescue/reconnaissance purposes vice firefighting, they will wear appropriate levels of protective clothing (see Section 8).
Section V: Health Hazard Data
AIRBORNE EXPOSURE LIMIT (AEL): The suggested permissible airborne exposure concentration for GA for an 8-hour workday or a 40 hour work week is an 8 hour time weight average (TWA) of 0.0001 mg/m3 (2 x 10-5 ppm). This value is based on the TWA of GA as proposed in the USaEHA Technical Guide 169, "Occupational Health Guildelines for the Evaluation and Control of Occupational Exposure to Nerve Agents, GA, GB, GD, and VX." To date, however, the Occupational Safety and Health Administration (OSHA) has not promulgated a permissible exposure concentration for GA.
EFFECTS OF OVEREXPOSURE:
GA is an anticholinesterase agent similar in action to GB. Although only about half as toxic as GB by inhalation, GA in low concentrations is more irritating to the eyes than GB.
The number and severity of symptoms which appear are dependent on the quantity, and rate of entry of the nerve agent which is introduced into the body. (Very small skin dosages sometimes cause local sweating and tremors with few other effects.)
Individuals poisoned by GA display apaproximately the same sequence of symptoms regardless of the route by which the poison enters the body (whether by inhalation, absorption, or ingestion). These symptoms, in normal order of appearance, runny nose; tightness of chest; dimness of vision and pin pointing of the eye pupils; difficulty in breathing; drooling and excessive sweating; nausea; vomiting, cramps, and involuntary defecation and urination; twitching, jerking, and staggering; and headaches, confusion, drowsiness, coma, and convulsion. These symptoms are followed by cessation of breathing and death.
Onset Time of Symptoms: Symptoms appear much more slowly from skin dosage than from respiratory dosage. Although skin absorption great enough to cause death may occur in 1 to 2 minutes, death may be delayed for 1 to 2 hours. Respiratory lethal dosages kill in 1 to 10 minutes, and liquid in the eye kills almost as rapidly.
Median Lethal Dosage, Animals: LD50 (monkey, percutaneous) = 9.3 mg/kg (shaved skin); LCt50 (monkey, inhalation) = 187 mg-min/m3 (t = 10)
Median Lethal Dosage, Man: LCt50 (man, inhalation) = 135 mg-min/m3 (t = 0.5-2 min) at RMV (Respiratory Minute Volume) of 15 1/min; 200 mg-min/m3 at RMV* of 10 1/min
GA is not listed by the International Agency for Research on Cancer (IARC), American Conference of Governmental Industrial Hygienists (ACGIH). Occupational Safety and Health Administration (OSHA), or National Toxicology Program (NTP) as a carcinogen.
EMERGENCY AND FIRST AID PROCEDURES:
• INHALATION: Hold breath until respiratory protective mask is donned. If severe signs of agent exposure appear (chest tightens, pupil construction, incoordination, etc.), immediately administer, in rapid succession, all three Nerve Agent Antidote Kit(s), Mark I injectors (or atropine if directed by the local physician). Injections using the Mark I kit injectors may be repeated at 5 to 20 minute intervals if signs and symptoms are progressing until three series of injections have been administered. No more injections will be given unless directed by medical personnel. In addition, a record will be maintained of all injections given. If breathing has stopped, give artificial respiration. Mouth-to-mouth resuscitation should be used when approved mask-bag or oxygen delivery systems are not available. Do not use mouth-to-mouth resuscitation when facial contamination exists. If breathing is difficult, administer oxygen. Seek medical attention IMMEDIATELY.
• EYE CONTACT: IMMEDIATELY flush eyes with water for 10-15 minutes then don respiratory protective mask. Although miosis (pinpointing of the pupils) may be an early sign of agent exposure, an injection will not be administered when miosis is the only sign present. Instead, the individual will be taken immediately to the medical treatment facility for observation.
• SKIN CONTACT: Don respiratory protection mask and remove contaminated clothing. Immediately wash contaminated skin with copious amounts of soap and water, 10% sodium carbonate solution, or 5% liquid household bleach. Rinse well with water to remove decontaminate. Administer an intramuscular injection with the MARK I kit injectors only if local sweating and muscular twitching symptoms are observed. Seek medical attention IMMEDIATELY.
• INGESTION: Do not induce vomiting. First symptoms are likely to be gastrointestinal. IMMEDIATELY administer 2 mg. intramuscular injection of the MARK I kit auto-injectors. Seek medical attention IMMEDIATELY.
Section VI: Reactivity Data
STABILITY: Stable
INCOMPATIBILITY: Not available
HAZARDOUS DECOMPOSITION: Decomposes within 6 months at 60 DEG C. Complete decomposition in 3-1/4 hours at 150 DEG C. May produce HCN. Oxides of nitrogen, oxides of phosphorus, carbon monoxide, and hydogen cyanide.
HAZARDOUS POLYMERIZATON: Not available
Section VII: Spill, Leak and Disposal Procedures
STEPS TO BE TAKEN IN CASE MATERIAL IS RELEASED OR SPILLED: If leaks or spills occur, only personnel in full protective clothing (see section 8) will remain in area. In case of personnel contamination see section V "Emergency and First Aid Instructions."
RECOMMENDED FIELD PROCEDURES:
Spills must be contained by covering with vermiculite, diatomaceious earth, clay, fine sand, sponges, and paper or cloth towels. This containment is followed by treatment with copious amounts of aqueous Sodium Hydroxide solution (a minimum 10 wt percent). Scoop up all material and place in a fully removable head drum with a high density polyethylene liner. The decontamination solution must be treated with excess bleach to destroy the CN formed during hydrolysis. Cover the contents with additional bleach before affixing the drum head. After sealing the head, the exterior of the drum shall be decontaminated and then labeled IAW EPA and DOT regulations.
All leaking containers shall be overpacked with vermiculite placed between the interior and exterior containers. Decontaminate and label IAW EPA and DOT regulations. Dispose of the material IAW waste disposal methods provided below. Conduct general area monitoring with an approved monitor (see Section 8) to confirm that the atmospheric concentrations do not exceed the airborne exposure limit (see Sections 2 and 8).
If 10 wt percent Sodium Hydroxide is not available then the following decontaminants may be used instead and are listed in order of preference: Decontamination Solution No. 2 (DS2), Sodium Carbonate and Supertropical Bleach Slurry (STB).
RECOMMENDED LABORATORY PROCEDURES:
A minimum of 56 grams of decon solution is required for each gram of GA. The decontamination solution is agitated while GA is added and the agitation is maintained for at least one hour. The resulting solution is allowed to react for 24 hours. At the end of 24 hours, the solution must be tritrated to a pH between 10 and 12. After completion of the 24 hour period, the decontamination solution must be treated with excess bleach (2.5 mole OC1-/mole GA) to destroy the CN formed during hydrolysis.
Scoop up all material and place in a fully removable head drum with a high density polyethylene liner. Cover the contents with additional bleach before affixing the drum head. All contaminated clothing will be placed in a fully removable head drum with a high density polyethylene liner. Cover the contents of the drum with decontaminating solution as above before affixing the drum head. After sealing the head, the exterior of the drum shall be decontaminated and then labeled IAW state, EPA and DOT regulations.
All leaking containers shall be overpacked with vermiculite placed between the interior and exterior containers. Decontaminate and label IAW State, EPA and DOT regulations. Conduct general area monitoring with an approved monitor (see Section 8) to confirm that the atmospheric concentrations do not exceed the airborne exposure limit (see Sections 2 and 8).
WASTE DISPOSAL METHOD: Open pit burning or burying of GA or items containing GA.
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Re: United States Dual-Use Exports to Iraq and Their Impact
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Material Safety Data Sheet -- Lethal Nerve Agent Sarin (GB)
Section I: General Information
MANUFACTURER'S NAME: Department of the Army
MANUFACTURER'S ADDRESS:
U.S. Army Chemical and Biological Defense Agency
Edgewood Research, Development and Engineering Center
ATTN: SCBRD-ODR-S
Aberdeen Proving Ground, MD 21010-5423
CAS REGISTRY NUMBER: 107-44-8 or 50642-23-4
CHEMICAL NAME AND SYMONYMS:
Phosphonofluoridic acid, methyl-, isopropyl ester
Phosphonofluoridic acid, methyl-, 1- methylethyl ester
ALTERNATE CHEMICAL NAMES:
Isopropyl methylphosphonofluoridate
Isopropyl ester of methylphosphonofluoridic acid
Methylisoproposfluorophosphine oxide
Isopropyl Methylfluorophosphonate
O-Isopropyl Methylisopropoxfluorophosphine oxide
O-Isopropyl Methylphosphonofluoridate
Methylfluorophosphonic acid, isopropyl ester
Isoproposymethylphosphonyl flouride
TRADE NAME AND SYNONYMS:
GB
Sarin
Zarin
CHEMICAL FAMILY: Fluorinated organophosphorous compound
FORMULA: C4 H10 F02 P
NFPA 704 SIGNAL:
Health - 4
Flammability - 1
Reactivity - 1
Section II: Composition
INGREDIENTS NAME: GB
FORMULA: C4 H10 FO2
PERCENTAGE: 100
AIRBORNE EXPOSURE LIMIT (AEL): 0.0001 mg/m3
Section III: Physical Data
BOILING POINT DEG F (DEG C): 316 (158)
VAPOR PRESSURE (mm hg): 2.9 @ 25 DEG C
VAPOR DENSITY (AIR=1): 4.86
SOLUBILITY IN WATER: Complete
SPECIFIC GRAVITY (H20=1): 1.0887 @ 25 DEG C
FREEZING/MELTING POINT: -56 DEG C
LIQUID DENSITY (g/cc): 1.0887 @ 25 DEG C/1.102 @ 20 DEG C
PERCENTAGE VOLATILE BY VOLUME: 22,000 m/m3 @ 25 DEG C/ 16,090 m/m3 @ 20 DEG C
APPEARANCE AND ODOR: Colorless liquid. Odorless in pure form.
Section IV: Fire and Explosion Data
FLASH POINT (METHOD USED): Did not flash to 280 DEG F
FLAMMABLE LIMIT: Not applicable
LOWER EMPLOSIVE LIMIT: Not available
UPPER EXPLOSIVE LIMIT: Not available
EXTINGUISING MEDIA: Water mist, fog, foam, CO2 - Avoid using extinguishing methods that will cause splashing or spreading of the GB
SPECIAL FIRE FIGHTING PROCEDURES:
GB will react with steam or water to produce toxic & corrosive vapors. All persons not engaged in extinguishing the fire should be evacuated. Fires involving GB should be contained to prevent contamination to uncontrolled areas. When responding to a fire alarm in buildings or areas containing agents, firefighting personnel clothing (without TAP clothing) during chemical agent firefighting and fire rescue operations.
Respiratory protection is required. Positive pressure, full facepiece, NIOSH-approved self- contained breathing apparatus (SCBA) will be worn where there is danger of oxygen deficiency and when directed by the fire chief or chemical accident/incident (CAI) operations officer. In cases where firefighters are responding to a chemical accident/incident for rescue/reconnaissance purposes vice firefighting, they will wear appropriate levels of protective clothing (see Section 8).
UNUSUAL FIRE AND EXPLOSION HAZARDS: Hydrogen may be present
Section V: Health Hazard Data
AIRBORNE EXPOSURE LIMIT (AEL): The permissible airborne exposure concentration for GB for an 6 hour workday or a 40 hour work week is an 8 hour time weight average (TWA) of 0.0001 mg/m3. This value is based on the TWA or GB which can be found in "AR 40-8, Occupational Health Guidelines for the Evaluation and Control of Occupational Exposure to Nerve Agents GA, GB, GD, and VX." To date, however, the Occupational Safety and Health Administration (OSHA) has not promulgated a permissible exposure concentration for GB.
EFFECTS OF OVEREXPOSURE: It is a lethal anticholinergic agent. Doses which are potentially life threatening may be only slightly larger than those producing minimal effects.
Route Form Effect Type Dosage
ocular vapor miosis ECt50 less than 2 mg-min/m3
inhalation vapor runny nose ECt50 less than 2 mg-min/m3
inhalation severe ICt50 35 mg-min/m3
incapacitation
inhalation vapor death LCt50 70 mg-min/m3
percutaneous liquid death LD50 1700 mg/70 kg man
Effective dosages for vapor are estimated for exposure durations of 2-10 minutes.
Symptoms of overexposure may occur within minutes or hours--depending upon dose. They include: miosis (constriction of pupils) and visual effects, headache and pressure sensation, runny nose and nasal congestion, salivation, tightness in the chest, nausea, vomiting, giddiness, anxiety, difficulty in thinking, difficulty sleeping, nightmares, muscle twitches, tremors, weakness, abdominal cramps, diarrhea, involuntary urination and defecation.
With severe exposure symptoms progress to convulsions and respiratory failure. GB is not listed by the International Agency for Research on Cancer (IARC), American Conference of Governmental Industrial Hygienists (ACGIH), Occupational Safety and Health Administration (OSHA), or National Toxicology Program (NTP) as a carcinogen.
EMERGENCY AND FIRST AID PROCEDURES:
• INHALATION: Hold breath until respiratory protective mask is donned. If severe signs of agent exposure appear (chest tightens, pupil constriction, incoordination, etc.), immediately administer, in rapid succession, all three Nerve Agent Antidote Kit(s), Mark I injectors (or atropine if directed by the local physician). Injections using the Mark I kit injectors may be repeated at 5 to 20 minute intervals if signs and symptoms are progressing until three series of injections have been administered. No more injections will be given unless directed by medical personnel. In addition, a record will be maintained of all injections given. If breathing has stopped, give artificial respiration. Mouth-to-mouth resuscitation should be used when approved mask-bag or oxygen delivery systems are not available. Do not use mouth-to-mouth resuscitation when facial contamination exists. If breathing is difficult, administer oxygen. Seek medical attention IMMEDIATELY.
• EYE CONTACT: Immediately flush eyes with water for 10-15 minutes, then don respiratory protective mask. Although miosis (pinpointing of the pupils) may be an early sign of agent exposure, an injection will not be administered when miosis is the only sign present. Instead, the individual will be taken IMMEDIATELY to the medical treatment facility for observation.
• SKIN CONTACT: Don respiratory protective mask and remove contaminated clothing. Immediately wash contaminated skin with copious amounts of soap and water, 10% sodium carbonate solution, or 5% liquid household bleach. Rinse well with water to remove decontaminant. Administer an intramuscular injection with the MARK I Kit injectors only if local sweating and muscular twitching symptoms are observed. SEEK MEDICAL ATTENTION IMMEDIATELY.
• INGESTION: Do not induce vomiting. First symptoms are likely to be gastrointestinal. Immediately administer an intramuscular injection of the MARK I kit auto-injectors. SEEK MEDICAL ATTENTION IMMEDIATELY.
Section VI: Reactivity Data
STABILITY: Stable when pure.
INCOMPATIBILITY: Attacks tin, magnesium, cadmium plated steel, some aluminums. Slight attack on copper, brass, lead, practically no attack on 1020 steel, Inconel & K-monel.
Hydrolyzes to form HF under acid conditions and isopropyl alcohol & polymers under basic conditions.
Section VII: Spill, Leak and Disposal Procedures
STEPS TO BE TAKEN IN CASE MATERIAL IS RELEASED OR SPILLED: If leak or spills occur, only personnel in full protective clothing (see section 8) will remain in area. In case of personnel contamination see section V "Emergency and First Aid Instructions."
RECOMMENDED FIELD PROCEDURES:
Spills must be contained by covering with vermiculite, diatomaceous earth clay, fine sand, sponges, and paper or cloth towels. Decontaminate with copious amounts of aqueous Sodium Hydroxide solution (a minimum 10 wt percent). Scoop up all material and place in a fully removable head drum with a high density polyethylene liner. Cover the contents of the drum with decontaminating solution as above before affixing the drum head.
After sealing the head, the exterior of the drum shall be decontaminated and then labeled IAW EPA and DOT regulations. All leaking containers shall be overpacked with vermiculite placed between the interior and exterior containers. Decontaminate and label IAW EPA and DOT regulations. Dispose of the material IAW waste disposal methods provided below. Dispose of material used to decontaminate exterior of drum IAW Federal, state and local regulations. Conduct general area monitoring with an approved monitor (see Section 8) to confirm that the atmospheric concentrations do not exceed the airborne exposure limit (see Sections 2 and 8).
If 10 wt. percent aqueous Sodium Hydroxide solution is not available then the following decontaminants may be used instead and are listed in the order of preference: Decontamination Solution No. 2 (DS2), Sodium Carbonate, and Supertropical Bleach Slurry (STB).
RECOMMENDED LABORATORY PROCEDURES:
A minimum of 56 grams of decon solution is required for each gram of GB. Decontaminant/agent solution is allowed to agitate for a minimum of one hour. Agitation is not necessary following the first hour. At the end of the one hour, the resulting solution should be adjusted to a pH greater than 11.5. If the pH is below 11.5, NaOH should be added until a pH above 11.5 can be maintained for 60 minutes.
An alternate solution for the decontamination of GB is 10 wt percent Sodium Carbonate in place of the 10 percent Sodium Hydroxide solution above. Continue with 56 grams of decon to 1 gram of agent. Agitate for one hour but allow three (3) hours for the reaction. The final pH should be adjusted to above 10. It is also permitted to substitute 5.25% Sodium Hypochlorite or 25 wt percent Monoethylamine (MEA) for the 10% Sodium Hydroxide solution above. MEA must be completely dissolved in water prior to addition of the agent. Continue with 56 grams of decon for each gram of GB and provide agitation for one hour. Continue with same ratios and time stipulations.
Scoop up all material and place in a fully removable head drum with a high density polyethylene liner. Cover the contents of the drum with decontaminating solution as above before affixing the drum head. After sealing the head, the exterior of the drum shall be decontaminated and then labeled IAW EPA and DOT regulations. All leaking containers shall be overpacked with vermiculite placed between the interior and exterior containers. Decontaminate and label IAW EPA and DOT regulations. Dispose of the material IAW waste disposal methods provided below. Dispose of material used to decontaminate exterior of drum IAW Federal, state and local regulations. Conduct general area monitoring with an approved monitor (see Section 8) to confirm that the atmospheric concentrations do not exceed the airborne exposure limit (see Sections 2 and 8).
WASTE DISPOSAL METHOD: Open pit burning or burying of GB or items containing or contaminated with GB in any quantity is prohibited. The detoxified GB using procedures above can be thermally destroyed by incineration in an EPA approved incinerator in accordance with appropriate provisions of Federal, state and local RCRA regulations.
Section VIII: Special Protection Information
RESPIRATORY PROTECTION:
Concentration Respiratory Protective Equipment
less than
0.0001 mg/m3 A full face piece, chemical canister, air purifying
protective mask will be onhand for escape. (The M9-, or
M40-series masks are acceptable for this purpose).
0.0001 to 0.2 mg/m3 A NIOSH/MSHA approved pressure demand full facepiece
SCBA or supplied air respirator with escape air cylinder
may be used.
Alternatively, a full facepiece, chemical canister air
purifying protective mask is acceptable for this purpose
(for example, M9-, M17-, or M40-series mask or other
mask certified as equivalent) is acceptable. (See DA PAM
385-61 for determination of appropriate level)
greater than
0.2 mg/m3 or unknown NIOSH/MSHA approved pressure demand full facepiece
SCBA suitable for use in high agent concentrations with
protective ensemble (see DA PAM 385-61 for examples).
VENTILATION: Local exhaust: Mandatory must be filtered or scrubbed to limit exit concentration to less than 0.0001 mg/m3 averaged over 8 hr/day indefinitely. Air emissions shall meet local, state and federal regulations.
• SPECIAL: Chemical laboratory hoods shall have an average inward face velocity of 100 linear feet per minute (1fpm) plus or minus 10% with the velocity at any point not deviating from the average face velocity by more than 20%. Existing laboratory hoods shall have an inward face velocity of 150 1fpm plus or minus 20 percent. Laboratory hoods shall be located such that cross drafts do not exceed 20 percent of the inward face velocity. A visual performance test utilizing smoke producing devices shall be performed in the assessment of the hood's ability to contain agent GB. Emergency backup power necessary. Hoods should be tested semi-annually or after modification or maintenance operations. Operations should be performed 20 cm inside hood face.
• OTHER: Recirculation of exhaust air from agent areas is prohibited. No connection is allowed between agent areas and other areas through ventilation system.
PROTECTIVE GLOVES: Butyl Glove M3 and M4, Norton, Chemical Protective Glove Set
EYE PROTECTION: Chemical goggles. For splash hazards use goggles and faceshield.
OTHER PROTECTIVE EQUIPMENT: For general lab work, gloves and lab coat shall be worn with M9, M17 or M40 mask readily available.
MONITORING:
Available monitoring equipment for agent GB is the M8/M9 Detector paper, detector ticket, blue band tube, M256/M256A1 kits, bubbler, Depot Area Air Monitoring System (DAAMS), Automatic Continuous Air Monitoring System (ACAMS), real time monitoring (RTM), Demilitarization Chemical Agent Concentrator (DCAC), M8/M43, M8A1/M43A2, Hydrogen Flame Photometric Emission Detector (HYPED), CAM-M1, Miniature Chemical Agent Monitor (MINICAM) and the Real Time Analytical Platform (RTAP).
Real-time, low-level monitors (with alarm) are required for GB operations. In their absence, an IDLH atmosphere must be presumed. Laboratory operations conducted in appropriately maintained and alarmed engineering controls require only periodic low-level monitoring.
Section IX: Special Precautions
PRECAUTIONS TO BE TAKEN IN HANDLING AND STORING: In handling, the buddy system will be incorporated. No smoking, eating and drinking in areas containing agent is permitted. Containers should be periodically inspected for leaks (either visually or by a detector kit). Stringent control over all personnel practices must be exercised. Decontamination equip shall be conveniently located. Exits must be designed to permit rapid evacuation. Chemical showers, eye-wash stations, and personal cleanliness facilities must be provided. Wash hands before meals and each worker will shower thoroughly with special attention given to hair, face, neck, and hands, using plenty of soap before leaving at the end of the work day.
OTHER PRECAUTIONS: Agents must be double contained in liquid and vapor tight containers when in storage or when outside of ventilation hood.
For additional information see "AR 385-61, The Army Toxic Chemical Agent Safety Program'" "DA PAM 385-61, Toxic Chemical Agent Safety Standards," and "AR 40-8, Occupational Health Guidelines for the Evaluation and Control of Occupational Exposure to Nerve Agents GA, GB, GD, and VX."
Section X: Transportation Data
PROPER SHIPPING NAME: Poisonous liquids, n.o.s.
DOT HAZARD CLASSIFICATION: 6.1 Packing Group I Hazard Zone A
DOT LABEL: Poison
DOT MARKING: Poisonous liquid, n.o.s. (Isopropyl methylphosphonofluoridate) UN2810
DOT PLACARD: Poison
PRECAUTIONS TO BE TAKEN IN TRANSPORTATION: Motor vehicles will be placarded regardless of quantity. Driver shall be given full and complete information regarding shipment and conditions in case of emergency.
AR 50-6 deals specifically with the shipment of chemical agents. Shipments of agent will be escorted in accordance with AR 740-32. EMERGENCY ACCIDENT PRECAUTIONS AND PROCEDURES: See sections IV, VII, and VIII.
Section I: General Information
MANUFACTURER'S NAME: Department of the Army
MANUFACTURER'S ADDRESS:
U.S. Army Chemical and Biological Defense Agency
Edgewood Research, Development and Engineering Center
ATTN: SCBRD-ODR-S
Aberdeen Proving Ground, MD 21010-5423
CAS REGISTRY NUMBER: 107-44-8 or 50642-23-4
CHEMICAL NAME AND SYMONYMS:
Phosphonofluoridic acid, methyl-, isopropyl ester
Phosphonofluoridic acid, methyl-, 1- methylethyl ester
ALTERNATE CHEMICAL NAMES:
Isopropyl methylphosphonofluoridate
Isopropyl ester of methylphosphonofluoridic acid
Methylisoproposfluorophosphine oxide
Isopropyl Methylfluorophosphonate
O-Isopropyl Methylisopropoxfluorophosphine oxide
O-Isopropyl Methylphosphonofluoridate
Methylfluorophosphonic acid, isopropyl ester
Isoproposymethylphosphonyl flouride
TRADE NAME AND SYNONYMS:
GB
Sarin
Zarin
CHEMICAL FAMILY: Fluorinated organophosphorous compound
FORMULA: C4 H10 F02 P
NFPA 704 SIGNAL:
Health - 4
Flammability - 1
Reactivity - 1
Section II: Composition
INGREDIENTS NAME: GB
FORMULA: C4 H10 FO2
PERCENTAGE: 100
AIRBORNE EXPOSURE LIMIT (AEL): 0.0001 mg/m3
Section III: Physical Data
BOILING POINT DEG F (DEG C): 316 (158)
VAPOR PRESSURE (mm hg): 2.9 @ 25 DEG C
VAPOR DENSITY (AIR=1): 4.86
SOLUBILITY IN WATER: Complete
SPECIFIC GRAVITY (H20=1): 1.0887 @ 25 DEG C
FREEZING/MELTING POINT: -56 DEG C
LIQUID DENSITY (g/cc): 1.0887 @ 25 DEG C/1.102 @ 20 DEG C
PERCENTAGE VOLATILE BY VOLUME: 22,000 m/m3 @ 25 DEG C/ 16,090 m/m3 @ 20 DEG C
APPEARANCE AND ODOR: Colorless liquid. Odorless in pure form.
Section IV: Fire and Explosion Data
FLASH POINT (METHOD USED): Did not flash to 280 DEG F
FLAMMABLE LIMIT: Not applicable
LOWER EMPLOSIVE LIMIT: Not available
UPPER EXPLOSIVE LIMIT: Not available
EXTINGUISING MEDIA: Water mist, fog, foam, CO2 - Avoid using extinguishing methods that will cause splashing or spreading of the GB
SPECIAL FIRE FIGHTING PROCEDURES:
GB will react with steam or water to produce toxic & corrosive vapors. All persons not engaged in extinguishing the fire should be evacuated. Fires involving GB should be contained to prevent contamination to uncontrolled areas. When responding to a fire alarm in buildings or areas containing agents, firefighting personnel clothing (without TAP clothing) during chemical agent firefighting and fire rescue operations.
Respiratory protection is required. Positive pressure, full facepiece, NIOSH-approved self- contained breathing apparatus (SCBA) will be worn where there is danger of oxygen deficiency and when directed by the fire chief or chemical accident/incident (CAI) operations officer. In cases where firefighters are responding to a chemical accident/incident for rescue/reconnaissance purposes vice firefighting, they will wear appropriate levels of protective clothing (see Section 8).
UNUSUAL FIRE AND EXPLOSION HAZARDS: Hydrogen may be present
Section V: Health Hazard Data
AIRBORNE EXPOSURE LIMIT (AEL): The permissible airborne exposure concentration for GB for an 6 hour workday or a 40 hour work week is an 8 hour time weight average (TWA) of 0.0001 mg/m3. This value is based on the TWA or GB which can be found in "AR 40-8, Occupational Health Guidelines for the Evaluation and Control of Occupational Exposure to Nerve Agents GA, GB, GD, and VX." To date, however, the Occupational Safety and Health Administration (OSHA) has not promulgated a permissible exposure concentration for GB.
EFFECTS OF OVEREXPOSURE: It is a lethal anticholinergic agent. Doses which are potentially life threatening may be only slightly larger than those producing minimal effects.
Route Form Effect Type Dosage
ocular vapor miosis ECt50 less than 2 mg-min/m3
inhalation vapor runny nose ECt50 less than 2 mg-min/m3
inhalation severe ICt50 35 mg-min/m3
incapacitation
inhalation vapor death LCt50 70 mg-min/m3
percutaneous liquid death LD50 1700 mg/70 kg man
Effective dosages for vapor are estimated for exposure durations of 2-10 minutes.
Symptoms of overexposure may occur within minutes or hours--depending upon dose. They include: miosis (constriction of pupils) and visual effects, headache and pressure sensation, runny nose and nasal congestion, salivation, tightness in the chest, nausea, vomiting, giddiness, anxiety, difficulty in thinking, difficulty sleeping, nightmares, muscle twitches, tremors, weakness, abdominal cramps, diarrhea, involuntary urination and defecation.
With severe exposure symptoms progress to convulsions and respiratory failure. GB is not listed by the International Agency for Research on Cancer (IARC), American Conference of Governmental Industrial Hygienists (ACGIH), Occupational Safety and Health Administration (OSHA), or National Toxicology Program (NTP) as a carcinogen.
EMERGENCY AND FIRST AID PROCEDURES:
• INHALATION: Hold breath until respiratory protective mask is donned. If severe signs of agent exposure appear (chest tightens, pupil constriction, incoordination, etc.), immediately administer, in rapid succession, all three Nerve Agent Antidote Kit(s), Mark I injectors (or atropine if directed by the local physician). Injections using the Mark I kit injectors may be repeated at 5 to 20 minute intervals if signs and symptoms are progressing until three series of injections have been administered. No more injections will be given unless directed by medical personnel. In addition, a record will be maintained of all injections given. If breathing has stopped, give artificial respiration. Mouth-to-mouth resuscitation should be used when approved mask-bag or oxygen delivery systems are not available. Do not use mouth-to-mouth resuscitation when facial contamination exists. If breathing is difficult, administer oxygen. Seek medical attention IMMEDIATELY.
• EYE CONTACT: Immediately flush eyes with water for 10-15 minutes, then don respiratory protective mask. Although miosis (pinpointing of the pupils) may be an early sign of agent exposure, an injection will not be administered when miosis is the only sign present. Instead, the individual will be taken IMMEDIATELY to the medical treatment facility for observation.
• SKIN CONTACT: Don respiratory protective mask and remove contaminated clothing. Immediately wash contaminated skin with copious amounts of soap and water, 10% sodium carbonate solution, or 5% liquid household bleach. Rinse well with water to remove decontaminant. Administer an intramuscular injection with the MARK I Kit injectors only if local sweating and muscular twitching symptoms are observed. SEEK MEDICAL ATTENTION IMMEDIATELY.
• INGESTION: Do not induce vomiting. First symptoms are likely to be gastrointestinal. Immediately administer an intramuscular injection of the MARK I kit auto-injectors. SEEK MEDICAL ATTENTION IMMEDIATELY.
Section VI: Reactivity Data
STABILITY: Stable when pure.
INCOMPATIBILITY: Attacks tin, magnesium, cadmium plated steel, some aluminums. Slight attack on copper, brass, lead, practically no attack on 1020 steel, Inconel & K-monel.
Hydrolyzes to form HF under acid conditions and isopropyl alcohol & polymers under basic conditions.
Section VII: Spill, Leak and Disposal Procedures
STEPS TO BE TAKEN IN CASE MATERIAL IS RELEASED OR SPILLED: If leak or spills occur, only personnel in full protective clothing (see section 8) will remain in area. In case of personnel contamination see section V "Emergency and First Aid Instructions."
RECOMMENDED FIELD PROCEDURES:
Spills must be contained by covering with vermiculite, diatomaceous earth clay, fine sand, sponges, and paper or cloth towels. Decontaminate with copious amounts of aqueous Sodium Hydroxide solution (a minimum 10 wt percent). Scoop up all material and place in a fully removable head drum with a high density polyethylene liner. Cover the contents of the drum with decontaminating solution as above before affixing the drum head.
After sealing the head, the exterior of the drum shall be decontaminated and then labeled IAW EPA and DOT regulations. All leaking containers shall be overpacked with vermiculite placed between the interior and exterior containers. Decontaminate and label IAW EPA and DOT regulations. Dispose of the material IAW waste disposal methods provided below. Dispose of material used to decontaminate exterior of drum IAW Federal, state and local regulations. Conduct general area monitoring with an approved monitor (see Section 8) to confirm that the atmospheric concentrations do not exceed the airborne exposure limit (see Sections 2 and 8).
If 10 wt. percent aqueous Sodium Hydroxide solution is not available then the following decontaminants may be used instead and are listed in the order of preference: Decontamination Solution No. 2 (DS2), Sodium Carbonate, and Supertropical Bleach Slurry (STB).
RECOMMENDED LABORATORY PROCEDURES:
A minimum of 56 grams of decon solution is required for each gram of GB. Decontaminant/agent solution is allowed to agitate for a minimum of one hour. Agitation is not necessary following the first hour. At the end of the one hour, the resulting solution should be adjusted to a pH greater than 11.5. If the pH is below 11.5, NaOH should be added until a pH above 11.5 can be maintained for 60 minutes.
An alternate solution for the decontamination of GB is 10 wt percent Sodium Carbonate in place of the 10 percent Sodium Hydroxide solution above. Continue with 56 grams of decon to 1 gram of agent. Agitate for one hour but allow three (3) hours for the reaction. The final pH should be adjusted to above 10. It is also permitted to substitute 5.25% Sodium Hypochlorite or 25 wt percent Monoethylamine (MEA) for the 10% Sodium Hydroxide solution above. MEA must be completely dissolved in water prior to addition of the agent. Continue with 56 grams of decon for each gram of GB and provide agitation for one hour. Continue with same ratios and time stipulations.
Scoop up all material and place in a fully removable head drum with a high density polyethylene liner. Cover the contents of the drum with decontaminating solution as above before affixing the drum head. After sealing the head, the exterior of the drum shall be decontaminated and then labeled IAW EPA and DOT regulations. All leaking containers shall be overpacked with vermiculite placed between the interior and exterior containers. Decontaminate and label IAW EPA and DOT regulations. Dispose of the material IAW waste disposal methods provided below. Dispose of material used to decontaminate exterior of drum IAW Federal, state and local regulations. Conduct general area monitoring with an approved monitor (see Section 8) to confirm that the atmospheric concentrations do not exceed the airborne exposure limit (see Sections 2 and 8).
WASTE DISPOSAL METHOD: Open pit burning or burying of GB or items containing or contaminated with GB in any quantity is prohibited. The detoxified GB using procedures above can be thermally destroyed by incineration in an EPA approved incinerator in accordance with appropriate provisions of Federal, state and local RCRA regulations.
Section VIII: Special Protection Information
RESPIRATORY PROTECTION:
Concentration Respiratory Protective Equipment
less than
0.0001 mg/m3 A full face piece, chemical canister, air purifying
protective mask will be onhand for escape. (The M9-, or
M40-series masks are acceptable for this purpose).
0.0001 to 0.2 mg/m3 A NIOSH/MSHA approved pressure demand full facepiece
SCBA or supplied air respirator with escape air cylinder
may be used.
Alternatively, a full facepiece, chemical canister air
purifying protective mask is acceptable for this purpose
(for example, M9-, M17-, or M40-series mask or other
mask certified as equivalent) is acceptable. (See DA PAM
385-61 for determination of appropriate level)
greater than
0.2 mg/m3 or unknown NIOSH/MSHA approved pressure demand full facepiece
SCBA suitable for use in high agent concentrations with
protective ensemble (see DA PAM 385-61 for examples).
VENTILATION: Local exhaust: Mandatory must be filtered or scrubbed to limit exit concentration to less than 0.0001 mg/m3 averaged over 8 hr/day indefinitely. Air emissions shall meet local, state and federal regulations.
• SPECIAL: Chemical laboratory hoods shall have an average inward face velocity of 100 linear feet per minute (1fpm) plus or minus 10% with the velocity at any point not deviating from the average face velocity by more than 20%. Existing laboratory hoods shall have an inward face velocity of 150 1fpm plus or minus 20 percent. Laboratory hoods shall be located such that cross drafts do not exceed 20 percent of the inward face velocity. A visual performance test utilizing smoke producing devices shall be performed in the assessment of the hood's ability to contain agent GB. Emergency backup power necessary. Hoods should be tested semi-annually or after modification or maintenance operations. Operations should be performed 20 cm inside hood face.
• OTHER: Recirculation of exhaust air from agent areas is prohibited. No connection is allowed between agent areas and other areas through ventilation system.
PROTECTIVE GLOVES: Butyl Glove M3 and M4, Norton, Chemical Protective Glove Set
EYE PROTECTION: Chemical goggles. For splash hazards use goggles and faceshield.
OTHER PROTECTIVE EQUIPMENT: For general lab work, gloves and lab coat shall be worn with M9, M17 or M40 mask readily available.
MONITORING:
Available monitoring equipment for agent GB is the M8/M9 Detector paper, detector ticket, blue band tube, M256/M256A1 kits, bubbler, Depot Area Air Monitoring System (DAAMS), Automatic Continuous Air Monitoring System (ACAMS), real time monitoring (RTM), Demilitarization Chemical Agent Concentrator (DCAC), M8/M43, M8A1/M43A2, Hydrogen Flame Photometric Emission Detector (HYPED), CAM-M1, Miniature Chemical Agent Monitor (MINICAM) and the Real Time Analytical Platform (RTAP).
Real-time, low-level monitors (with alarm) are required for GB operations. In their absence, an IDLH atmosphere must be presumed. Laboratory operations conducted in appropriately maintained and alarmed engineering controls require only periodic low-level monitoring.
Section IX: Special Precautions
PRECAUTIONS TO BE TAKEN IN HANDLING AND STORING: In handling, the buddy system will be incorporated. No smoking, eating and drinking in areas containing agent is permitted. Containers should be periodically inspected for leaks (either visually or by a detector kit). Stringent control over all personnel practices must be exercised. Decontamination equip shall be conveniently located. Exits must be designed to permit rapid evacuation. Chemical showers, eye-wash stations, and personal cleanliness facilities must be provided. Wash hands before meals and each worker will shower thoroughly with special attention given to hair, face, neck, and hands, using plenty of soap before leaving at the end of the work day.
OTHER PRECAUTIONS: Agents must be double contained in liquid and vapor tight containers when in storage or when outside of ventilation hood.
For additional information see "AR 385-61, The Army Toxic Chemical Agent Safety Program'" "DA PAM 385-61, Toxic Chemical Agent Safety Standards," and "AR 40-8, Occupational Health Guidelines for the Evaluation and Control of Occupational Exposure to Nerve Agents GA, GB, GD, and VX."
Section X: Transportation Data
PROPER SHIPPING NAME: Poisonous liquids, n.o.s.
DOT HAZARD CLASSIFICATION: 6.1 Packing Group I Hazard Zone A
DOT LABEL: Poison
DOT MARKING: Poisonous liquid, n.o.s. (Isopropyl methylphosphonofluoridate) UN2810
DOT PLACARD: Poison
PRECAUTIONS TO BE TAKEN IN TRANSPORTATION: Motor vehicles will be placarded regardless of quantity. Driver shall be given full and complete information regarding shipment and conditions in case of emergency.
AR 50-6 deals specifically with the shipment of chemical agents. Shipments of agent will be escorted in accordance with AR 740-32. EMERGENCY ACCIDENT PRECAUTIONS AND PROCEDURES: See sections IV, VII, and VIII.
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Re: United States Dual-Use Exports to Iraq and Their Impact
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Material Safety Data Sheet -- Lethal Nerve Agents Somain (GD and Thickened GD)
Section I: General Information
MANUFACTURER'S NAME: Department of the Army
MANUFACTURER'S ADDRESS:
U.S. Army Armament, Munitions and Chemical Command
Chemical Research, Development and Engineering Center
ATTN: SMCCR-CMS-E
Aberdeen Proving Ground, MD 21010-5423
CAS REGISTRY NUMBER: 96-64-0 or 50642-24-5
CHEMICAL NAME: Phosphonofluoridic acid, methyl-, 1, 2, 2-trimethylpropyl ester
ALTERNATE CHEMICAL NAMES:
• Pinacolyl methylphosphonofluoridate
• 1,2,2-Trimethylpropyl methylphosphonofluoridate
• Methylpinacolyloxyfluorophosphine oxide
• Pinacolyloxymethylphosphonyl flouride
• Pinacolyl methanefluorophosphonate
• Methylfluoropinacolylphosphonate
• Fluoromethylpinacolyloxyphosphine Oxide
• Methylpinacolyloxyphosphonyl flouride
• Pinacolyl methylfluorophosphonate
• 1,2,2,-Trimethylpropoxyfluoromethylphosphine oxide
TRADE NAME AND SYNONYMS:
• GD
• EA 1210
• Soman, Zoman
• PFMP
CHEMICAL FAMILY: Fluorinated organophosphorus compound
FORMULA: C7 H16 F02 P
NFPA 704 SIGNAL:
• Health - 4
• Flammability - 1
• Reactivity - 1
Section II: Hazardous Ingredients
INGREDIENTS FORMULA PERCENTAGE AIRBORNE
BY WEIGHT EXPOSURE LIMIT
GD C7 H16 FOP 100 0.00003 mg/m3
Return to Top of Page
Section III: Physical Data
BOILING POINT DEG F (DEG C): (198 DEC C) 388 DEG F
VAPOR PRESSURE: 0.40 mm Hg @ 25 DEG C
VAPOR DENSITY (AIR=1): 6.3
SOLUBILITY IN WATER: Moderate
SPECIFIC GRAVITY (H20=1): 1.022 @ 25 DEG C
VOLATILITY: 3900 mg/m3 @ 25 DEC C
MELTING POINT: -42 DEG C
APPEARANCE AND ODOR: When pure, colorless liquid with fruity odor. With impurities, amber or dark brown, with oil of camphor odor
Section IV: Fire and Explosion Data
FLASHPOINT: 121 DEG C (Open Cup)
FLAMMABILITY LIMITS: Unknown
LOWER EXPLOSIVE LIMIT: Not applicable
UPPER EXPLOSIVE LIMIT: Not applicable
EXTINGUISING MEDIA: Water, fog, foam, CO2 - Avoid using extinguishing methods that will cause splashing or spreading of the GD.
SPECIAL FIRE FIGHTING PROCEDURES:
Fires involving GD should be contained to prevent contamination of uncontrolled areas. All persons not engaged in extinguishing the fire should be evacuated immediately. Contact with GD or its vapors can be fatal. When responding to a fire alarm in buildings or areas containing agents, firefighting personnel should wear full firefighter protective clothing (without TAP clothing) during chemical agent firefighting and fire rescue operations.
Respiratory protection is required. Positive pressure, full facepiece, NIOSH approved self contained breathing apparatus (SCBA) will be worn where there is danger of oxygen deficiency and when directed by the fire chief or chemical accident/incident (CAI) operations officer. The M9 or M17 series mask may be worn in lieu of SCBA when there is no danger of oxygen deficiency. In cases where firefighter are responding to a chemical accident/incident for rescue/reconnaissance purposes vice firefighting, they will wear appropriate levels of protective clothing (see Section 8).
UNUSUAL FIRE AND EXPLOSION HAZARDS: Hydrogen produced by the corrosive vapors reacting with metals, concrete, etc., may be present.
Section V: Health Hazard Data
AIRBORNE EXPOSURE LIMIT (AEL): The suggested permissible airborne exposure concentration of GD for an 8 hour workday or a 40 hour work week is an 8 hour time weighted average (TWA) of 0.00003 mg/m3 (2 x 10-5 ppm). This value is based on the TWA of GB as proposed in the USaEHA Technical Guide No. 169, "Occupational Health Guidelines for the Evaluation and Control of Occupational Exposure to Nerve Agents GA, GB, GD, and VX." To date, however, the Occupational Safety and Health Administration (OSHA) has not promulgated permissible exposure concentration for GD.
EFFECTS OF OVEREXPOSURE: GD is a lethal anticholinesterase agent with the median lethal dose in man being: LCt50 (inhalation) = 70 mg min/m3 (t = 10 min); LD50 (PC, bare skin) = 0.35 g/man (70 kg).
1. One to several minutes after overexposure to airborne GD the following acute symptoms appear:
1. LOCAL EFFECTS (lasting 1-15 days, increase with dose)
1. On eyes: Miosis (constriction of pupils); redness, pressure sensation on eyes.
2. By inhalation: Rhinorrhea (runny nose), nasal congestion, tightness in chest, wheezing, salivation, nausea, vomiting
2. SYSTEMIC EFFECTS (increases with dose): When inhaled GD will cause excessive secretion causing coughing/breathing difficulty: salivation and sweating: vomiting, diarrhea; stomach cramps; involuntary urination/defecation; generalized muscle twitching/muscle cramps; CNS depression including anxiety, restlessness, giddiness, insomnia, excessive dreaming and nightmares. With more severe exposure, also headache, tremor, drowsiness, concentration difficulty, memory impairment, confusion, unsteadiness on standing or walking, and progressing to death.
2. After exposure to liquid GD, the following acute symptoms appear:
1. LOCAL EFFECTS:
1. On eyes: Miosis (constriction of pupils); redness, pressure sensation on eyes.
2. By ingestion: salivation, anorexia, nausea, vomiting, abdominal cramps, diarrhea, involuntary defecation, heartburn.
3. On skin: Sweating, muscle twitching
2. Chronic exposure to GD causes forgetfulness, thinking difficulty, vision disturbances, muscular aches/pains. Although certain organophosphate pesticides have been shown to be teratogenic in animals, these effects have not been documented in carefully controlled toxicological evaluations for GD.
GD presently is not listed by the International Agency for Research on Cancer (IARC), National Toxicology Program (NTP), Occupational Safety and Health Administration (OSHA), or American Conference of Governmental Industrial Hygienists (ACGIH) as a carcinogen.
EMERGENCY AND FIRST AID PROCEDURES:
• INHALATION: Hold breath until respiratory protective mask is donned. If severe signs of agent exposure appear (chest tightens, pupil constriction, incoordination, etc.), immediately administer, in rapid succession, all three Nerve Agent Antidote Kit(s), Mark I injectors (or atropine if directed by the local physician). Injections using the Mark I kit injectors may be repeated at 5 to 20 minute intervals if signs and symptoms are progressing until three series of injections have been administered. No more injections will be given unless directed by medical personnel. In addition, a record will be maintained of all injections given. If breathing has stopped, give artificial respiration. Mouth-to-mouth resuscitation should be used when approved mask-bag of oxygen delivery systems are not available. Do not use mouth-to-mouth resuscitation when facial contamination exists. If breathing is difficult, administer oxygen. Seek medical attention IMMEDIATELY.
• EYE CONTACT: IMMEDIATELY flush eyes with water for 10-15 minutes, then don respiratory protective mask. Although miosis (pinpointing of the pupils) may be an early sign of agent exposure, an injection will not be administered when miosis is the only sign present. Instead, the individual will be taken IMMEDIATELY to the medical treatment facility for observation.
• SKIN CONTACT: Don respsiratory protective mask and remove contaminated clothing. Immediately wash contaminated skin with copious amounts of soap and water, 10% sodium carbonate solution, or 5% liquid household bleach. Rinse well with water to remove decontaminant. Administer nerve agent antidote kit, Mark I, only if local sweating and muscular twitching symptoms are present. Seek medical attention IMMEDIATELY.
• INGESTION: Do not induce vomiting. First symptoms are likely to be gastronintestinal. IMMEDIATELY administer Nerve Agent Antidote kit, Mark I. Seek medical attention immediately.
Section VI: Reactivity Data
STABILITY: Stable after storage in steel for 3 months at 65 Deg. C. GD corrodes steel at the rate of 1 x 10-5 inch/month.
GD will hydrolyze to form HF--H-H-O-CH3 and (CH3) 3-C-C-O-P-OH
HAZARDOUS POLYMERIZATION: Will not occur.
Section VII: Spill, Leak and Disposal Procedures
STEPS TO BE TAKEN IN CASE MATERIAL IS RELEASED OR SPILLED: If leak or spills occur, only personnel in full protective clothing (see Section 8) will remain in area. In case of personnel contamination, see Section V "Emergency and First Aid Procedures."
RECOMMENDED FIELD PROCEDURES:
Spills must be contained by covering with vermiculite, diatomaceous earth, clay, fine sand, sponges and paper or cloth towels. This containment is followed by treatment with copious amounts of aqueous Sodium Hydroxide solution (a minimum of 10 percent). Scoop up all material and place in a fully removable head drum with a high density polyethylene liner. Cover the contents of the drum with decontaminating solution as above before affixing the drum head. After sealing the head, the exterior of the drum shall be decontaminated and then labeled IAW EPA and DOT regulations.
All leaking containers shall be overpacked with vermiculite placed between the interior and exterior containers. Decontaminate and label IAW EPA and DOT regulations. Dispose of the material IAW waste disposal methods provided below. Dispose of material used to decontaminate exterior of drum IAW Federal, state and local regulations. Contaminated clothing will be placed in a fully removable head drum with a high density polyethylene liner and the contents shall be covered with decontaminating solution as above before affixing the drum head. Conduct general area monitoring to confirm that the atmospheric concentrations do not exceed the exposure limits (see Section 8).
If 10 wt percent aqueous Sodium Hydroxide solution is not available then the following decontaminants may be used instead and are listed in the order of preference: Decontaminating Solution No. 2 (DS2), Sodium Carbonate, and Supertropical Tropical Bleach Slurry (STB).
RECOMMENDED LABORATORY PROCEDURES:
A minimum of 55 grams of decon solution is required per gram of GD. Decontaminant/agent solution is allowed to agitate for a minimum of one hour. Agitation is not necessary following the first hour provided a single phase is obtained. At the end of the first hour the pH should be checked and adjusted up to 11.5 with additional NaOH as required.
An alternate solution for the decontamination of GD is 10 percent Sodium Carbonate in place of the 10 percent Sodium Hydroxide solution above. Continue with 55 grams of decon per gram of GD. Agitate for one hour and allow to react for 3 hours. At the end of the third hour adjust the pH to above 10. It is also permitted to substitute 5.25% Sodium Hypochlorite for the 10% Sodium Hydroxide solution above. Continue with 55 grams of decon per gram of GD. Agitate for one hour and allow to react for 3 hours then adjust the pH to above 10.
Scoop up alll material and place in a fully removable head and a high density polyethylene liner. Cover the contents with additional decontaminating solution before affixing the drum head. After sealing the head, the exterior of the drum shall be decontaminated and then labeled IAW EPA and DOT regulations. All contaminated clothing will be placed in a fully removable head drum with a high density polyethylene liner.
Cover the contents of the drum with decontaminating solution as above before affixing the drum head. After sealing the head, the exterior of the drum shall be decontaminated and then labeled IAW EPA and DOT regulations. All leaking containers shall be overpacked with vermiculite placed between the interior and exterior containers. Decontaminate and label IAW EPA and DOT regulations. Dispose of the material IAW waste disposal methods provided below. Conduct general area monitoring to confirm that the atmospheric concentrations do not exceed the exposure limits (see Section 8).
WASTE DISPOSAL METHOD: Open pit burning or burying of GD or items containing or contaminated with GD in any quantity is prohibited. The detoxified GD (using procedures above) can be thermally destroyed by incineration in an EPA approved incinerator in accordance with appropriate provisions of Federal, state and local RCRA regulations.
NOTE: Some states define decontaminated surety material as a RCRA Hazardous Waste.
Section VIII: Special Protection Informatoon
RESPIRATORY PROTECTION:
GD Concentration Respiratory Protective Equipment
Less than 0.00003 mg/m3 M9, M17, or M40 series mask shall be available for escape
as necessary
0.00003 mg/m3 to 0.06 mg/m3 M9, or M40 series mask with Level A or Level B ensemble
(see AMCR 385-131 for determination of appropriate
level).
Demilitarization Protective Emsemble (DPE), or
Toxicological Agent Protective Ensemble Self-Contained
(TAPES), used with prior approval from AMC Field Safety
Activity.
Greater than 0.06 mg/m3 or DPE or TAPES used with prior approval from AMC Field
unknown Field Safety Activity
NOTE: When DPE or TAPES is not available the M9 or
M40 series mask with Level A protective ensemble can be
used. However, use time shall be restricted to the extent
operationally feasible, and may not exceed one hour.
As an additional precaution, the cuffs of the sleeves and the
legs of the M3 suit shall be taped to the gloves and boots
respectively to reduce aspiration.
• Local Exhaust: Mandatory. Must be filtered or scrubbed to limit exit conc. to <.00001 mg/m3 (averaged over 8 hr/day, indefinitely).
• Special: Chemical laboratory hoods shall have an average inward face velocity of 100 linear feet per minute (lfpm) + 10 percent with the velocity at any point not deviating from the average face velocity by more than 20 percent. Laboratory hoods shall be located such that cross-drafts do not exceed 20 percent of the inward face velocity. A visual performance test utilizing smoke- producing devices shall be performed in assessing the ability of the hood to contain agent GD.
• Emergency back-up power necessary: Hoods should be tested semi-annually or after modification or maintenance operations. Operations should be performed 20 cm inside hood face.
• Other: Recirculation of exhaust air from agent areas is prohibited. No connection between agent areas and other areas through ventilation system is permitted.
PROTECTIVE GLOVES: Butyl Glove M3 and M4; Northon, Chemical Protective Glove Set
EYE PROTECTION: Chemical Goggles. For splash hazards use goggles and faceshield.
OTHER PROTECTIVE EQUIPMENT: Full protective clothing will consist of M9 mask and hood, butyl rubber suit (M3), M2A1 butyl boots, M3 and M4 gloves, unimpregnated underwear, or demilitarization protective ensemble (DPE). For laboratory operations, wear lab coats and have a protective mask readily available.
MONITORING: Available monitoring equipment for agent GD is the Automatic Chemical Agent Detector Alarm (ACADA), bubblers (GC method), and Chemical Agent Monitor (CAM).
Section IX: Special Precautions
PRECAUTIONS TO BE TAKEN IN HANDLING AND STORING: In handling GD, the buddy system will be incorporated. No smoking, eating or drinking is permitted in areas containing agent GD. Containers should be periodically inspected for leaks (either visually or by a detector kit) and prior to transferring the containers from storage to work areas. Stringent control over all personnel practices must be exercised. Decontamination equipment shall be conveniently located. Exits must be designed to permit rapid evacuation. Chemical showers, eyewash stations, and personal cleanliness facilities shall be provided. Wash hands before meals and each worker will shower thoroughly with special attention given to hair, face, neck, and hands, using plenty of soap before leaving at the end of the workday.
OTHER PRECAUTIONS: Agent must be double-contained in liquid and vapor-tight containers when in storage or when outside of the ventilation hood.
For additional information, see AMC-R 385-131, "Safety Regulations for Chemical Agents H, HD, GB, and VX" and USaEHA Technical Guide No. 169, "Occupational Health Guidelines for the Evaluation and Control of Occupational Exposure to Nerve Agents GA, GB, GD, and VX."
Section X: Transportation Data
PROPER SHIPPING NAME: Poisonous liquid, n.o.s.
DOT HAZARD CLASSIFICATION: Poison A
DOT LABEL: Poison gas
DOT MARKING: Poisonous liquid, n.o.s. (Pinacolyl methylphosphonofluoridate) NA 1955
DOT PLACARD: POISON GA
EMERGENCY ACCIDENT PRECAUTIONS AND PROCEDURES: See Section IV, VII and VIII.
PRECAUTIONS TO BE TAKEN IN TRANSPORTATION:
Motor vehicles will be placarded regardless of quantity. Driver shall be given full and complete information regarding shipment and conditions in case of emergency.
AR 50-6 deals specifically with the shipment of chemical agents. Shipments of agent will be escorted in accordance with AR 740-32.
While the Chemical Research Development and Engineering Center, Department of the Army believes that the data contained herein are factual and the opinions expressed are those of qualified experts regarding the results of the tests conducted, the data are not to be taken as a warranty or representation for which the Department of the Army or Chemical Research Development Engineering Center assumes legal responsibility. They are offered solely for your consideration, investigation, and verification. Any use of these data and information must be determined by the user to be in accordance with applicable Federal, State, and local laws and regulations.
Addendum A: Physiological Effects
ACUTE PHYSIOLOGICAL EFFECTS:
Site of Action Signs and Symptoms
Muscarine-like-
Pupils Miosis, marked, usually maximal (pinpoint),
sometimes unequal.
Ciliary body Frontal headache, eye pain on focusing, slight
dimness of vision, occasional nausea and vomiting.
Conjunctivae Hyperemia
Nasal mucous membranes Rhinorrhea, hyperemia
Bronchial tree Tighness in chest, sometimes with prolonged
wheezing, expiration suggestive of broncho-
constriction or increased secretion, cough.
Following Systemic Absorption
Bronchial tree Tightness in chest, with prolonged wheezing,
expiration suggestive of broncho-constriction or
increased secretion, dyspnea, slight pain in chest,
increased, bronchial secretion, cough, pulmonary
edema, cyanosis.
Gastrointestinal Anorexia, nausea, vomiting, abdominal cramps,
epigastric and substernal tightness (cardiospasm)
with "heartburn" and eructation, diarrhea, tenesmus,
involuntary defecation.
Sweat glands Increased sweating
Salivary glands Increased salivation
Lacrimal glands Increased lacrimation
Heart Slight bradycardia
Pupils Slight miosis, occasionally unequal, later maximal
miosis (pinpoint).
Ciliary body Blurring of vision
Bladder Frequent, involuntary micturition
Nicotine-like
Striated muscle Easy fatigue, mild weakness, muscular twitching,
fasciculations, cramps, generalized weakness,
including muscles of respiration, with dyspnea and
cyanosis.
Sympathetic ganglia Pallor, occasional elevation of blood pressure.
Central Nervous system Giddiness, tension, anxiety, jitteriness, restlessness,
emotional lability, excessive dreaming, insomnia,
nightmares, headaches, tremor, withdrawal and
depression, bursts of slow waves of elevated
voltage in EEG, especially on over-ventilation,
drowsiness, difficult concentration, slowness on
recall, confusion, slurred speech, ataxia,
generalized weakness, coma, with absence of
reflexes, Cheyne-Stokes respirations, convulsions,
depression of respiratory and circulatory centers,
with dyspnea, cyanosis, and fall in blood pressure.
CHRONIC PHYSIOLOGICAL EFFECTS:
• Acute Exposure: If recovery from nerve agent poisoning occurs, it will be complete unless anoxia or convulsions have gone unchecked so long that irreversible central nervous system changes due to anoxemia have occurred.
• Chronic Exposure
• The inhibition of cholinesterase enzymes throughout the body by nerve agents is more or less irreversible so that their effects are prolonged. Until the tissue cholinesterase enzymes are restored to normal activity, probably by very slow regeneration over a period of weeks or 2 to 3 months if damage is severe there is a period of increased susceptibility to the effects of another exposure to any nerve agent. During this period the effects of repeated exposures are cumulative; after a single exposure, daily exposure to concentrations of a nerve agent insufficient to produce symptoms may result in the onset of symptoms after several days. Continued daily exposure may be followed by increasingly severe effects. After symptoms subside, increased susceptibility persists for one to several days. The degree of exposure required to produce recurrence of symptoms, and the severity of these symptoms, depend on duration of exposure and time intervals between exposures. Increased susceptibility is not limited to the particular nerve agent initially absorbed.
• Estimates have been made for the times as which 50% of exposed subjects would be affected (Et50's) at median incapacitating doses. These are presented below
______________________________________________________________________________
Et50 Degree of ICt50 Exposure Time
Effectiveness
______________________________________________________________________________
min mg min/m3 min
1.5 Moderate 27 0.5
3.0 Incap. 27 2.0
6.0 40 10.0
1.0 Severe 37 0.5
3.8 Incap. 37 2.0
7.8 56 10.0
2.0 Very 47 0.5
4.5 Severe 47 2.0
9.5 Incap. 72 10.0
6.5 Death 70 5.0
9.0 70 2.0
13.5 103 10.0
______________________________________________________________________________
• Exposure to high concentrations of nerve agent may bring on incoordination, mental confusion and collapse so rapidly that the casualty cannot perform self-aid. If this happens, the man nearest to him will give first aid.
• Onset Time of Symptoms
______________________________________________________________________________
When Effects
Types of Route Description Appear After
Effects Absorption of Effects Exposure
______________________________________________________________________________
Vapor Lungs Rhinorrhea, nasal Hyperemia One to several minutes
Local tightness in chest, wheezing
Vapor Eyes Miosis, conjectival hyperemia One to several minutes
Local eye pain, frontal headache
Vapor Lungs or Muscarine-like, nicotine-like Less than 1 min. to a few
min.
Systemic eyes and central nervous system after moderate or marked
effects. (See 2a above) exposure: about 30 min. after
mild exposure
Liquid Eyes Same as vapor effects Instantly
Local
Liquid Ingestion Gastrointestinal. (See 2a above). About 30 min. after ingestion
Local
Liquid Skin Local sweating and muscular 3 min to 2 hours
Local twitching
Liquid Lungs See 2a above Several minutes
Sytemic
Liquid Eyes Same as for vapor Several minutes
Systemic
Liquid Skin Generalized sweating 15 minutes to 2 hours
Systemic
Liquid Ingestion Gastrointestinal (see 2a above) 15 minutes to 2 hours
Systemic
______________________________________________________________________________
Duration of Effects After
______________________________________________________________________________
Types of Route of Mild Severe
Effects Absorption Exposure Exposure
______________________________________________________________________________
Vapor Lungs A few hours 1 to 2 days
Local
Vapor Eyes Miosis - 3 to 14 days
Local 24 hours 2 to 5 days
Vapor Lungs or eyes Several hours 8 days
Systemic
Liquid Eyes Similar to effects
Local of vapor
Liquid Ingestion 3 days 5 days
Local
Liquid Skin 3 days 5 days
Local
Liquid Lungs 1 to 5 days
Systemic
Liquid Eyes 2 to 4 days
Systemic
Liquid Skin 2 to 5 days
Systemic
Liquid Ingestion 3 to 5 days
Systemic
Addendum B: First Aid Procedures
1. Exposed personnel will be removed immediately to an uncontaminated atmosphere. Personnel handling casualty cases will give consideration to their own safety and will take precautions and employ the prerequisite protective equipment to avoid becoming exposed themselves.
CAUTION: Due to the rapid effects of nerve agents, it is extremely important that decontamination of personnel not be delayed by attempting to blot off excessive agent prior to decontamination with sodium hypochlorite.
2. The causality will then be decontaminated by washing the contaminated areas with commercial liquid household bleach (nominal 5% solution hyprchlorite or 10 percent sodium carbonate solution) and flushing with clean water. Mask will be left on the victim until decontamination has been completed unless it has been determined that areas of the face were contaminated and the mask must be removed to facilitate decontamination. After decontamination, the contaminated clothing will be removed and skin contamination washed away. If possible, decontamination will be completed before the casualty is taken to the aid station of medical facility.
CAUTION: Care must be taken when decontaminating facial areas to avoid getting the hypochlorite into the eye or mouth. Only clean water shall be used when flushing the eyes or mouth. Skin surfaces decontaminated with bleach should be thoroughly flushed with water to prevent skin irritation from the bleach.
3. If there is no apparent breathing, artifical resuscitation will be started immediately (mouth-to-mouth, or with mechanical resuscitator). The situation will dictate method of choice, e.g., contaminated face. Do not use mouth-to-mouth resuscitation when facial contamination exists. When appropriate and trained personnel are available, cardiopulmonary resuscitation (CPR) may be necessary.46. An individual who has received a known agent exposure or who exhibits definite signs or symptoms of agent exposure shall be given an intramuscular injection immediately with the MARK I kit auto-injectors.
1. Some of the early symptoms of a vapor exposure may be rhinorrhea (runny nose) and/or tightness in the chest with shortness of breath (bronchial constriction).
2. Some of the early symptoms of a percutaneous exposure may be local muscular twitching or sweating at the area of exposure followed by nausea or vomiting.
3. Although myosis (pin-pointing of the pupils) may be an early sign of agent exposure, an injection shall not be administered when myosis is the only sign present. Instead, the individual shall be taken immediately to the medical facility for observation.
4. Injections using the MARK I kit injectors (or atropine only if directed by the local physician) may be repeated at 5 to 20 minute intervals if signs and symptoms are progressing until three series of injections have been administered. No more injections will be given unless directed by medical personnel. In addition, a record will maintained of all injections given.
5. Administer, in rapid succession, all three MARK I kit injectors (or atropine if directed by the local physician) in the case of SEVERE signs of agent exposure.
5. If indicated, CPR should be started immediately. Mouth-to-mouth resuscitation should be used when approved mask-bag or oxygen delivery systems are not available. Do not use mouth-to-mouth resuscitation when facial contamination exists.
CAUTION: Atropine does not act as a prophylactic and shall not be administered until an agent exposure has been ascertained.
Addendum C: Additional Information for Thickened GD
TRADE NAME AND SYNONYMS: Thickened GD, TGD
HAZARDOUS INGREDIENTS: K125 (acryloid copolymer, 5%) is used to thicken the GD. K125 is not known to be a hazardous material except in a finely divided, powder form.
PHYSICAL DATA: Essential the same as GD except for viscosity. The viscosity of TGD is approximately 1180 centistokes.
FIRE AND EXPLOSION DATA: Same as GD
HEALTH HAZARD DATA: Same as GD except for skin contact. For skin contact, don respiratory protective mask and remove contaminated clothing. Immediately scrape the TGD from the skin surface, then wash the contaminated surface with acetone. Administer Nerve Agent Antidote Kit, MARK I, only if local sweating and muscular twitching symptoms are observed. Seek medical attention IMMEDIATELY.
SPILL, LEAK AND DISPOSAL PROCEDURES: If spills or leaks of TGD occur, follow the same procedure as those for GD, but add the following step: Since TGD is not water soluble, dissolve the TGD in acetone prior to introducing any decontaminating solution. Containment of TGD is generally not necessary. Spilled TGD can be carefully scraped off the contaminated surface and placed in a drum with a fully removable head and a high density, polyethylene lining. The TGD can then be decontaminated after it has been dissolved in acetone, using the same procedures as for GD. Contaminated surfaces should be treated with acetone, then decontaminated using the same procedures as for GD.
SPECIAL PROTECTION INFORMATION: Same as GD.
SPECIAL PRECAUTIONS: Same as GD with the following addition. Handling the TGD requires careful observation of the "stringers" (elastic, thread-like attachments) formed when the agents are transferred or dispensed. These stringers must be broken cleanly before moving the contaminating device or dispensing device to another location, or unwanted contamination of a working surface will result.
TRANSPORTATION DATA: Same as GD.
Section I: General Information
MANUFACTURER'S NAME: Department of the Army
MANUFACTURER'S ADDRESS:
U.S. Army Armament, Munitions and Chemical Command
Chemical Research, Development and Engineering Center
ATTN: SMCCR-CMS-E
Aberdeen Proving Ground, MD 21010-5423
CAS REGISTRY NUMBER: 96-64-0 or 50642-24-5
CHEMICAL NAME: Phosphonofluoridic acid, methyl-, 1, 2, 2-trimethylpropyl ester
ALTERNATE CHEMICAL NAMES:
• Pinacolyl methylphosphonofluoridate
• 1,2,2-Trimethylpropyl methylphosphonofluoridate
• Methylpinacolyloxyfluorophosphine oxide
• Pinacolyloxymethylphosphonyl flouride
• Pinacolyl methanefluorophosphonate
• Methylfluoropinacolylphosphonate
• Fluoromethylpinacolyloxyphosphine Oxide
• Methylpinacolyloxyphosphonyl flouride
• Pinacolyl methylfluorophosphonate
• 1,2,2,-Trimethylpropoxyfluoromethylphosphine oxide
TRADE NAME AND SYNONYMS:
• GD
• EA 1210
• Soman, Zoman
• PFMP
CHEMICAL FAMILY: Fluorinated organophosphorus compound
FORMULA: C7 H16 F02 P
NFPA 704 SIGNAL:
• Health - 4
• Flammability - 1
• Reactivity - 1
Section II: Hazardous Ingredients
INGREDIENTS FORMULA PERCENTAGE AIRBORNE
BY WEIGHT EXPOSURE LIMIT
GD C7 H16 FOP 100 0.00003 mg/m3
Return to Top of Page
Section III: Physical Data
BOILING POINT DEG F (DEG C): (198 DEC C) 388 DEG F
VAPOR PRESSURE: 0.40 mm Hg @ 25 DEG C
VAPOR DENSITY (AIR=1): 6.3
SOLUBILITY IN WATER: Moderate
SPECIFIC GRAVITY (H20=1): 1.022 @ 25 DEG C
VOLATILITY: 3900 mg/m3 @ 25 DEC C
MELTING POINT: -42 DEG C
APPEARANCE AND ODOR: When pure, colorless liquid with fruity odor. With impurities, amber or dark brown, with oil of camphor odor
Section IV: Fire and Explosion Data
FLASHPOINT: 121 DEG C (Open Cup)
FLAMMABILITY LIMITS: Unknown
LOWER EXPLOSIVE LIMIT: Not applicable
UPPER EXPLOSIVE LIMIT: Not applicable
EXTINGUISING MEDIA: Water, fog, foam, CO2 - Avoid using extinguishing methods that will cause splashing or spreading of the GD.
SPECIAL FIRE FIGHTING PROCEDURES:
Fires involving GD should be contained to prevent contamination of uncontrolled areas. All persons not engaged in extinguishing the fire should be evacuated immediately. Contact with GD or its vapors can be fatal. When responding to a fire alarm in buildings or areas containing agents, firefighting personnel should wear full firefighter protective clothing (without TAP clothing) during chemical agent firefighting and fire rescue operations.
Respiratory protection is required. Positive pressure, full facepiece, NIOSH approved self contained breathing apparatus (SCBA) will be worn where there is danger of oxygen deficiency and when directed by the fire chief or chemical accident/incident (CAI) operations officer. The M9 or M17 series mask may be worn in lieu of SCBA when there is no danger of oxygen deficiency. In cases where firefighter are responding to a chemical accident/incident for rescue/reconnaissance purposes vice firefighting, they will wear appropriate levels of protective clothing (see Section 8).
UNUSUAL FIRE AND EXPLOSION HAZARDS: Hydrogen produced by the corrosive vapors reacting with metals, concrete, etc., may be present.
Section V: Health Hazard Data
AIRBORNE EXPOSURE LIMIT (AEL): The suggested permissible airborne exposure concentration of GD for an 8 hour workday or a 40 hour work week is an 8 hour time weighted average (TWA) of 0.00003 mg/m3 (2 x 10-5 ppm). This value is based on the TWA of GB as proposed in the USaEHA Technical Guide No. 169, "Occupational Health Guidelines for the Evaluation and Control of Occupational Exposure to Nerve Agents GA, GB, GD, and VX." To date, however, the Occupational Safety and Health Administration (OSHA) has not promulgated permissible exposure concentration for GD.
EFFECTS OF OVEREXPOSURE: GD is a lethal anticholinesterase agent with the median lethal dose in man being: LCt50 (inhalation) = 70 mg min/m3 (t = 10 min); LD50 (PC, bare skin) = 0.35 g/man (70 kg).
1. One to several minutes after overexposure to airborne GD the following acute symptoms appear:
1. LOCAL EFFECTS (lasting 1-15 days, increase with dose)
1. On eyes: Miosis (constriction of pupils); redness, pressure sensation on eyes.
2. By inhalation: Rhinorrhea (runny nose), nasal congestion, tightness in chest, wheezing, salivation, nausea, vomiting
2. SYSTEMIC EFFECTS (increases with dose): When inhaled GD will cause excessive secretion causing coughing/breathing difficulty: salivation and sweating: vomiting, diarrhea; stomach cramps; involuntary urination/defecation; generalized muscle twitching/muscle cramps; CNS depression including anxiety, restlessness, giddiness, insomnia, excessive dreaming and nightmares. With more severe exposure, also headache, tremor, drowsiness, concentration difficulty, memory impairment, confusion, unsteadiness on standing or walking, and progressing to death.
2. After exposure to liquid GD, the following acute symptoms appear:
1. LOCAL EFFECTS:
1. On eyes: Miosis (constriction of pupils); redness, pressure sensation on eyes.
2. By ingestion: salivation, anorexia, nausea, vomiting, abdominal cramps, diarrhea, involuntary defecation, heartburn.
3. On skin: Sweating, muscle twitching
2. Chronic exposure to GD causes forgetfulness, thinking difficulty, vision disturbances, muscular aches/pains. Although certain organophosphate pesticides have been shown to be teratogenic in animals, these effects have not been documented in carefully controlled toxicological evaluations for GD.
GD presently is not listed by the International Agency for Research on Cancer (IARC), National Toxicology Program (NTP), Occupational Safety and Health Administration (OSHA), or American Conference of Governmental Industrial Hygienists (ACGIH) as a carcinogen.
EMERGENCY AND FIRST AID PROCEDURES:
• INHALATION: Hold breath until respiratory protective mask is donned. If severe signs of agent exposure appear (chest tightens, pupil constriction, incoordination, etc.), immediately administer, in rapid succession, all three Nerve Agent Antidote Kit(s), Mark I injectors (or atropine if directed by the local physician). Injections using the Mark I kit injectors may be repeated at 5 to 20 minute intervals if signs and symptoms are progressing until three series of injections have been administered. No more injections will be given unless directed by medical personnel. In addition, a record will be maintained of all injections given. If breathing has stopped, give artificial respiration. Mouth-to-mouth resuscitation should be used when approved mask-bag of oxygen delivery systems are not available. Do not use mouth-to-mouth resuscitation when facial contamination exists. If breathing is difficult, administer oxygen. Seek medical attention IMMEDIATELY.
• EYE CONTACT: IMMEDIATELY flush eyes with water for 10-15 minutes, then don respiratory protective mask. Although miosis (pinpointing of the pupils) may be an early sign of agent exposure, an injection will not be administered when miosis is the only sign present. Instead, the individual will be taken IMMEDIATELY to the medical treatment facility for observation.
• SKIN CONTACT: Don respsiratory protective mask and remove contaminated clothing. Immediately wash contaminated skin with copious amounts of soap and water, 10% sodium carbonate solution, or 5% liquid household bleach. Rinse well with water to remove decontaminant. Administer nerve agent antidote kit, Mark I, only if local sweating and muscular twitching symptoms are present. Seek medical attention IMMEDIATELY.
• INGESTION: Do not induce vomiting. First symptoms are likely to be gastronintestinal. IMMEDIATELY administer Nerve Agent Antidote kit, Mark I. Seek medical attention immediately.
Section VI: Reactivity Data
STABILITY: Stable after storage in steel for 3 months at 65 Deg. C. GD corrodes steel at the rate of 1 x 10-5 inch/month.
GD will hydrolyze to form HF--H-H-O-CH3 and (CH3) 3-C-C-O-P-OH
HAZARDOUS POLYMERIZATION: Will not occur.
Section VII: Spill, Leak and Disposal Procedures
STEPS TO BE TAKEN IN CASE MATERIAL IS RELEASED OR SPILLED: If leak or spills occur, only personnel in full protective clothing (see Section 8) will remain in area. In case of personnel contamination, see Section V "Emergency and First Aid Procedures."
RECOMMENDED FIELD PROCEDURES:
Spills must be contained by covering with vermiculite, diatomaceous earth, clay, fine sand, sponges and paper or cloth towels. This containment is followed by treatment with copious amounts of aqueous Sodium Hydroxide solution (a minimum of 10 percent). Scoop up all material and place in a fully removable head drum with a high density polyethylene liner. Cover the contents of the drum with decontaminating solution as above before affixing the drum head. After sealing the head, the exterior of the drum shall be decontaminated and then labeled IAW EPA and DOT regulations.
All leaking containers shall be overpacked with vermiculite placed between the interior and exterior containers. Decontaminate and label IAW EPA and DOT regulations. Dispose of the material IAW waste disposal methods provided below. Dispose of material used to decontaminate exterior of drum IAW Federal, state and local regulations. Contaminated clothing will be placed in a fully removable head drum with a high density polyethylene liner and the contents shall be covered with decontaminating solution as above before affixing the drum head. Conduct general area monitoring to confirm that the atmospheric concentrations do not exceed the exposure limits (see Section 8).
If 10 wt percent aqueous Sodium Hydroxide solution is not available then the following decontaminants may be used instead and are listed in the order of preference: Decontaminating Solution No. 2 (DS2), Sodium Carbonate, and Supertropical Tropical Bleach Slurry (STB).
RECOMMENDED LABORATORY PROCEDURES:
A minimum of 55 grams of decon solution is required per gram of GD. Decontaminant/agent solution is allowed to agitate for a minimum of one hour. Agitation is not necessary following the first hour provided a single phase is obtained. At the end of the first hour the pH should be checked and adjusted up to 11.5 with additional NaOH as required.
An alternate solution for the decontamination of GD is 10 percent Sodium Carbonate in place of the 10 percent Sodium Hydroxide solution above. Continue with 55 grams of decon per gram of GD. Agitate for one hour and allow to react for 3 hours. At the end of the third hour adjust the pH to above 10. It is also permitted to substitute 5.25% Sodium Hypochlorite for the 10% Sodium Hydroxide solution above. Continue with 55 grams of decon per gram of GD. Agitate for one hour and allow to react for 3 hours then adjust the pH to above 10.
Scoop up alll material and place in a fully removable head and a high density polyethylene liner. Cover the contents with additional decontaminating solution before affixing the drum head. After sealing the head, the exterior of the drum shall be decontaminated and then labeled IAW EPA and DOT regulations. All contaminated clothing will be placed in a fully removable head drum with a high density polyethylene liner.
Cover the contents of the drum with decontaminating solution as above before affixing the drum head. After sealing the head, the exterior of the drum shall be decontaminated and then labeled IAW EPA and DOT regulations. All leaking containers shall be overpacked with vermiculite placed between the interior and exterior containers. Decontaminate and label IAW EPA and DOT regulations. Dispose of the material IAW waste disposal methods provided below. Conduct general area monitoring to confirm that the atmospheric concentrations do not exceed the exposure limits (see Section 8).
WASTE DISPOSAL METHOD: Open pit burning or burying of GD or items containing or contaminated with GD in any quantity is prohibited. The detoxified GD (using procedures above) can be thermally destroyed by incineration in an EPA approved incinerator in accordance with appropriate provisions of Federal, state and local RCRA regulations.
NOTE: Some states define decontaminated surety material as a RCRA Hazardous Waste.
Section VIII: Special Protection Informatoon
RESPIRATORY PROTECTION:
GD Concentration Respiratory Protective Equipment
Less than 0.00003 mg/m3 M9, M17, or M40 series mask shall be available for escape
as necessary
0.00003 mg/m3 to 0.06 mg/m3 M9, or M40 series mask with Level A or Level B ensemble
(see AMCR 385-131 for determination of appropriate
level).
Demilitarization Protective Emsemble (DPE), or
Toxicological Agent Protective Ensemble Self-Contained
(TAPES), used with prior approval from AMC Field Safety
Activity.
Greater than 0.06 mg/m3 or DPE or TAPES used with prior approval from AMC Field
unknown Field Safety Activity
NOTE: When DPE or TAPES is not available the M9 or
M40 series mask with Level A protective ensemble can be
used. However, use time shall be restricted to the extent
operationally feasible, and may not exceed one hour.
As an additional precaution, the cuffs of the sleeves and the
legs of the M3 suit shall be taped to the gloves and boots
respectively to reduce aspiration.
• Local Exhaust: Mandatory. Must be filtered or scrubbed to limit exit conc. to <.00001 mg/m3 (averaged over 8 hr/day, indefinitely).
• Special: Chemical laboratory hoods shall have an average inward face velocity of 100 linear feet per minute (lfpm) + 10 percent with the velocity at any point not deviating from the average face velocity by more than 20 percent. Laboratory hoods shall be located such that cross-drafts do not exceed 20 percent of the inward face velocity. A visual performance test utilizing smoke- producing devices shall be performed in assessing the ability of the hood to contain agent GD.
• Emergency back-up power necessary: Hoods should be tested semi-annually or after modification or maintenance operations. Operations should be performed 20 cm inside hood face.
• Other: Recirculation of exhaust air from agent areas is prohibited. No connection between agent areas and other areas through ventilation system is permitted.
PROTECTIVE GLOVES: Butyl Glove M3 and M4; Northon, Chemical Protective Glove Set
EYE PROTECTION: Chemical Goggles. For splash hazards use goggles and faceshield.
OTHER PROTECTIVE EQUIPMENT: Full protective clothing will consist of M9 mask and hood, butyl rubber suit (M3), M2A1 butyl boots, M3 and M4 gloves, unimpregnated underwear, or demilitarization protective ensemble (DPE). For laboratory operations, wear lab coats and have a protective mask readily available.
MONITORING: Available monitoring equipment for agent GD is the Automatic Chemical Agent Detector Alarm (ACADA), bubblers (GC method), and Chemical Agent Monitor (CAM).
Section IX: Special Precautions
PRECAUTIONS TO BE TAKEN IN HANDLING AND STORING: In handling GD, the buddy system will be incorporated. No smoking, eating or drinking is permitted in areas containing agent GD. Containers should be periodically inspected for leaks (either visually or by a detector kit) and prior to transferring the containers from storage to work areas. Stringent control over all personnel practices must be exercised. Decontamination equipment shall be conveniently located. Exits must be designed to permit rapid evacuation. Chemical showers, eyewash stations, and personal cleanliness facilities shall be provided. Wash hands before meals and each worker will shower thoroughly with special attention given to hair, face, neck, and hands, using plenty of soap before leaving at the end of the workday.
OTHER PRECAUTIONS: Agent must be double-contained in liquid and vapor-tight containers when in storage or when outside of the ventilation hood.
For additional information, see AMC-R 385-131, "Safety Regulations for Chemical Agents H, HD, GB, and VX" and USaEHA Technical Guide No. 169, "Occupational Health Guidelines for the Evaluation and Control of Occupational Exposure to Nerve Agents GA, GB, GD, and VX."
Section X: Transportation Data
PROPER SHIPPING NAME: Poisonous liquid, n.o.s.
DOT HAZARD CLASSIFICATION: Poison A
DOT LABEL: Poison gas
DOT MARKING: Poisonous liquid, n.o.s. (Pinacolyl methylphosphonofluoridate) NA 1955
DOT PLACARD: POISON GA
EMERGENCY ACCIDENT PRECAUTIONS AND PROCEDURES: See Section IV, VII and VIII.
PRECAUTIONS TO BE TAKEN IN TRANSPORTATION:
Motor vehicles will be placarded regardless of quantity. Driver shall be given full and complete information regarding shipment and conditions in case of emergency.
AR 50-6 deals specifically with the shipment of chemical agents. Shipments of agent will be escorted in accordance with AR 740-32.
While the Chemical Research Development and Engineering Center, Department of the Army believes that the data contained herein are factual and the opinions expressed are those of qualified experts regarding the results of the tests conducted, the data are not to be taken as a warranty or representation for which the Department of the Army or Chemical Research Development Engineering Center assumes legal responsibility. They are offered solely for your consideration, investigation, and verification. Any use of these data and information must be determined by the user to be in accordance with applicable Federal, State, and local laws and regulations.
Addendum A: Physiological Effects
ACUTE PHYSIOLOGICAL EFFECTS:
Site of Action Signs and Symptoms
Muscarine-like-
Pupils Miosis, marked, usually maximal (pinpoint),
sometimes unequal.
Ciliary body Frontal headache, eye pain on focusing, slight
dimness of vision, occasional nausea and vomiting.
Conjunctivae Hyperemia
Nasal mucous membranes Rhinorrhea, hyperemia
Bronchial tree Tighness in chest, sometimes with prolonged
wheezing, expiration suggestive of broncho-
constriction or increased secretion, cough.
Following Systemic Absorption
Bronchial tree Tightness in chest, with prolonged wheezing,
expiration suggestive of broncho-constriction or
increased secretion, dyspnea, slight pain in chest,
increased, bronchial secretion, cough, pulmonary
edema, cyanosis.
Gastrointestinal Anorexia, nausea, vomiting, abdominal cramps,
epigastric and substernal tightness (cardiospasm)
with "heartburn" and eructation, diarrhea, tenesmus,
involuntary defecation.
Sweat glands Increased sweating
Salivary glands Increased salivation
Lacrimal glands Increased lacrimation
Heart Slight bradycardia
Pupils Slight miosis, occasionally unequal, later maximal
miosis (pinpoint).
Ciliary body Blurring of vision
Bladder Frequent, involuntary micturition
Nicotine-like
Striated muscle Easy fatigue, mild weakness, muscular twitching,
fasciculations, cramps, generalized weakness,
including muscles of respiration, with dyspnea and
cyanosis.
Sympathetic ganglia Pallor, occasional elevation of blood pressure.
Central Nervous system Giddiness, tension, anxiety, jitteriness, restlessness,
emotional lability, excessive dreaming, insomnia,
nightmares, headaches, tremor, withdrawal and
depression, bursts of slow waves of elevated
voltage in EEG, especially on over-ventilation,
drowsiness, difficult concentration, slowness on
recall, confusion, slurred speech, ataxia,
generalized weakness, coma, with absence of
reflexes, Cheyne-Stokes respirations, convulsions,
depression of respiratory and circulatory centers,
with dyspnea, cyanosis, and fall in blood pressure.
CHRONIC PHYSIOLOGICAL EFFECTS:
• Acute Exposure: If recovery from nerve agent poisoning occurs, it will be complete unless anoxia or convulsions have gone unchecked so long that irreversible central nervous system changes due to anoxemia have occurred.
• Chronic Exposure
• The inhibition of cholinesterase enzymes throughout the body by nerve agents is more or less irreversible so that their effects are prolonged. Until the tissue cholinesterase enzymes are restored to normal activity, probably by very slow regeneration over a period of weeks or 2 to 3 months if damage is severe there is a period of increased susceptibility to the effects of another exposure to any nerve agent. During this period the effects of repeated exposures are cumulative; after a single exposure, daily exposure to concentrations of a nerve agent insufficient to produce symptoms may result in the onset of symptoms after several days. Continued daily exposure may be followed by increasingly severe effects. After symptoms subside, increased susceptibility persists for one to several days. The degree of exposure required to produce recurrence of symptoms, and the severity of these symptoms, depend on duration of exposure and time intervals between exposures. Increased susceptibility is not limited to the particular nerve agent initially absorbed.
• Estimates have been made for the times as which 50% of exposed subjects would be affected (Et50's) at median incapacitating doses. These are presented below
______________________________________________________________________________
Et50 Degree of ICt50 Exposure Time
Effectiveness
______________________________________________________________________________
min mg min/m3 min
1.5 Moderate 27 0.5
3.0 Incap. 27 2.0
6.0 40 10.0
1.0 Severe 37 0.5
3.8 Incap. 37 2.0
7.8 56 10.0
2.0 Very 47 0.5
4.5 Severe 47 2.0
9.5 Incap. 72 10.0
6.5 Death 70 5.0
9.0 70 2.0
13.5 103 10.0
______________________________________________________________________________
• Exposure to high concentrations of nerve agent may bring on incoordination, mental confusion and collapse so rapidly that the casualty cannot perform self-aid. If this happens, the man nearest to him will give first aid.
• Onset Time of Symptoms
______________________________________________________________________________
When Effects
Types of Route Description Appear After
Effects Absorption of Effects Exposure
______________________________________________________________________________
Vapor Lungs Rhinorrhea, nasal Hyperemia One to several minutes
Local tightness in chest, wheezing
Vapor Eyes Miosis, conjectival hyperemia One to several minutes
Local eye pain, frontal headache
Vapor Lungs or Muscarine-like, nicotine-like Less than 1 min. to a few
min.
Systemic eyes and central nervous system after moderate or marked
effects. (See 2a above) exposure: about 30 min. after
mild exposure
Liquid Eyes Same as vapor effects Instantly
Local
Liquid Ingestion Gastrointestinal. (See 2a above). About 30 min. after ingestion
Local
Liquid Skin Local sweating and muscular 3 min to 2 hours
Local twitching
Liquid Lungs See 2a above Several minutes
Sytemic
Liquid Eyes Same as for vapor Several minutes
Systemic
Liquid Skin Generalized sweating 15 minutes to 2 hours
Systemic
Liquid Ingestion Gastrointestinal (see 2a above) 15 minutes to 2 hours
Systemic
______________________________________________________________________________
Duration of Effects After
______________________________________________________________________________
Types of Route of Mild Severe
Effects Absorption Exposure Exposure
______________________________________________________________________________
Vapor Lungs A few hours 1 to 2 days
Local
Vapor Eyes Miosis - 3 to 14 days
Local 24 hours 2 to 5 days
Vapor Lungs or eyes Several hours 8 days
Systemic
Liquid Eyes Similar to effects
Local of vapor
Liquid Ingestion 3 days 5 days
Local
Liquid Skin 3 days 5 days
Local
Liquid Lungs 1 to 5 days
Systemic
Liquid Eyes 2 to 4 days
Systemic
Liquid Skin 2 to 5 days
Systemic
Liquid Ingestion 3 to 5 days
Systemic
Addendum B: First Aid Procedures
1. Exposed personnel will be removed immediately to an uncontaminated atmosphere. Personnel handling casualty cases will give consideration to their own safety and will take precautions and employ the prerequisite protective equipment to avoid becoming exposed themselves.
CAUTION: Due to the rapid effects of nerve agents, it is extremely important that decontamination of personnel not be delayed by attempting to blot off excessive agent prior to decontamination with sodium hypochlorite.
2. The causality will then be decontaminated by washing the contaminated areas with commercial liquid household bleach (nominal 5% solution hyprchlorite or 10 percent sodium carbonate solution) and flushing with clean water. Mask will be left on the victim until decontamination has been completed unless it has been determined that areas of the face were contaminated and the mask must be removed to facilitate decontamination. After decontamination, the contaminated clothing will be removed and skin contamination washed away. If possible, decontamination will be completed before the casualty is taken to the aid station of medical facility.
CAUTION: Care must be taken when decontaminating facial areas to avoid getting the hypochlorite into the eye or mouth. Only clean water shall be used when flushing the eyes or mouth. Skin surfaces decontaminated with bleach should be thoroughly flushed with water to prevent skin irritation from the bleach.
3. If there is no apparent breathing, artifical resuscitation will be started immediately (mouth-to-mouth, or with mechanical resuscitator). The situation will dictate method of choice, e.g., contaminated face. Do not use mouth-to-mouth resuscitation when facial contamination exists. When appropriate and trained personnel are available, cardiopulmonary resuscitation (CPR) may be necessary.46. An individual who has received a known agent exposure or who exhibits definite signs or symptoms of agent exposure shall be given an intramuscular injection immediately with the MARK I kit auto-injectors.
1. Some of the early symptoms of a vapor exposure may be rhinorrhea (runny nose) and/or tightness in the chest with shortness of breath (bronchial constriction).
2. Some of the early symptoms of a percutaneous exposure may be local muscular twitching or sweating at the area of exposure followed by nausea or vomiting.
3. Although myosis (pin-pointing of the pupils) may be an early sign of agent exposure, an injection shall not be administered when myosis is the only sign present. Instead, the individual shall be taken immediately to the medical facility for observation.
4. Injections using the MARK I kit injectors (or atropine only if directed by the local physician) may be repeated at 5 to 20 minute intervals if signs and symptoms are progressing until three series of injections have been administered. No more injections will be given unless directed by medical personnel. In addition, a record will maintained of all injections given.
5. Administer, in rapid succession, all three MARK I kit injectors (or atropine if directed by the local physician) in the case of SEVERE signs of agent exposure.
5. If indicated, CPR should be started immediately. Mouth-to-mouth resuscitation should be used when approved mask-bag or oxygen delivery systems are not available. Do not use mouth-to-mouth resuscitation when facial contamination exists.
CAUTION: Atropine does not act as a prophylactic and shall not be administered until an agent exposure has been ascertained.
Addendum C: Additional Information for Thickened GD
TRADE NAME AND SYNONYMS: Thickened GD, TGD
HAZARDOUS INGREDIENTS: K125 (acryloid copolymer, 5%) is used to thicken the GD. K125 is not known to be a hazardous material except in a finely divided, powder form.
PHYSICAL DATA: Essential the same as GD except for viscosity. The viscosity of TGD is approximately 1180 centistokes.
FIRE AND EXPLOSION DATA: Same as GD
HEALTH HAZARD DATA: Same as GD except for skin contact. For skin contact, don respiratory protective mask and remove contaminated clothing. Immediately scrape the TGD from the skin surface, then wash the contaminated surface with acetone. Administer Nerve Agent Antidote Kit, MARK I, only if local sweating and muscular twitching symptoms are observed. Seek medical attention IMMEDIATELY.
SPILL, LEAK AND DISPOSAL PROCEDURES: If spills or leaks of TGD occur, follow the same procedure as those for GD, but add the following step: Since TGD is not water soluble, dissolve the TGD in acetone prior to introducing any decontaminating solution. Containment of TGD is generally not necessary. Spilled TGD can be carefully scraped off the contaminated surface and placed in a drum with a fully removable head and a high density, polyethylene lining. The TGD can then be decontaminated after it has been dissolved in acetone, using the same procedures as for GD. Contaminated surfaces should be treated with acetone, then decontaminated using the same procedures as for GD.
SPECIAL PROTECTION INFORMATION: Same as GD.
SPECIAL PRECAUTIONS: Same as GD with the following addition. Handling the TGD requires careful observation of the "stringers" (elastic, thread-like attachments) formed when the agents are transferred or dispensed. These stringers must be broken cleanly before moving the contaminating device or dispensing device to another location, or unwanted contamination of a working surface will result.
TRANSPORTATION DATA: Same as GD.
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Re: United States Dual-Use Exports to Iraq and Their Impact
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Material Safety Data Sheet -- Lethal Nerve Agent VX
Section I: General Information
MANUFACTURER'S NAME: Department of the Army
MANUFACTURER'S ADDRESS:
U.S. Army Armament, Munitions and Chemical Command
Chemical Research, Development and Engineering Center
ATTN: SMCCR-CMS-E
Aberdeen Proving Ground, MD 21010-5423
CAS REGISTRY NUMBER: 50782-69-9, 51848-47-6, 53800-40-1, 70938-84-0
CHEMICAL NAME: Phosphonothioic acid, methyl-, S-(2bis(1-methylethylamino)ethyl) 0-ethyl ester
ALTERNATE CHEMICAL NAMES:
• O-ethyl S-(2-diisopropylaminoethyl) methylphosphonothioate
• S-2-Diisopropylaminoethyl O-ethyl methylphosphonothioate
• S-2 (2-Diisopropylamino)ethyl) O-ethyl methylphosphonothiolate
• O-ethyl S-(2-diisoproplyaminoethy) methylphosphonothioate
• O-ethyl S-(2-diisoproplyaminoethy) methylthiolphosphonoate
TRADE NAME AND SYNONYMS:
• VS
• EA 1701
• TX60
CHEMICAL FAMILY: Sulfinated organophosphorus compound
FORMULA: C11 H26 N 02 P S
NFPA 704 SIGNAL:
• Health - 4
• Flammability - 1
• Reactivity - 1
Section II: Composition
INGREDIENTS FORMULA PERCENTAGE AIRBORNE
NAME BY WEIGHT EXPOSURE LIMIT
VX C11H26N02PS 100 .00001 mg/m3
Section III: Physical Data
BOILING POINT DEG F (DEG C): 568 (298)
VAPOR PRESSURE (mm Hg): 0.0007 @ 25 DEG C
VAPOR DENSITY (AIR=1): 9.2
SOLUBILITY IN WATER: Moderate
APPEARANCE AND ODOR: Colorless to straw colored liquid & odorless, similar in appearance to motor oil.
Section IV: Fire and Explosion Data
FLASHPOINT: 159 DEG C (McCutchan-Young)
FLAMMABILITY LIMITS: (% by volume): Not available
LOWER EXPLOSIVE LIMIT: Not applicable
UPPER EXPLOSIVE LIMIT: Not applicable
EXTINGUISING MEDIA: Water mist, fog, foam, CO2 - Avoid using extinguishing methods that will cause splashing or spreading of the VX.
SPECIAL FIRE FIGHTING PROCEDURES:
All persons not engaged in extinguishing the fire should be immediately evacuated from the area. Fires involving VX should be contained to prevent contamination to uncontrolled areas. When responding to a fire alarm in buildings or areas containing agents, firefighting personnel should wear full firefighter protective clothing (without TAP clothing) during chemical agent firefighting and fire rescue operations.
Respiratory protection is required. Positive pressure, full facepiece, NIOSH-approved self contained breathing apparatus (SCBA) will be worn where there is danger of oxygen deficiency and when directed by the fire chief of chemical accident/incident (CAI) operations officer. The M9 or M17 series mask may be worn in lieu of SCBA when there is no danger of oxygen deficiency. In cases where firefighters are responding to a chemical accident/incident for rescue/reconnaissance purposes vice firefighting, they will wear appropriate levels of protective clothing (see Section 8).
Do not breathe fumes. Skin contact with V-agents must be avoided at all times. Although the fire may destroy most of the agent, care must still be taken to assure the agent or contaminated liquids do not further contaminate other areas or sewers. Contact with VX or VX vapors can be fatal.
UNUSUAL FIRE AND EXPLOSION HAZARDS: None known.
Section V: Health Hazard Data
RECOMMENDED EXPOSURE LIMIT (REL):
The suggested permissible airborne exposure concentration of VX for an 8 hour workday or a 40 hour work week is an 8 hour time weighted average (TWA) of 0.00001 mg/m3 (9 x 10-7 ppm). This value is based on the TWA of VX as proposed in the USAEHA Technical Guide No. 169, "Occupational Health Guidelines for the Evaluation and Control of Occupational Exposure to Nerve Agents GA, GB, GD, and VX." To date, however, the Occupational Safety and Health Administration (OSHA) has not promulgated permissible exposure concentration for VX.
VX is not listed by the International Agency for Research on Cancer (IARC), American Conference of Governmental Industrial Hygienists (ACGIH), Occupational Safety and Health Administration (OSHA), or National Toxicology Program (NTP) as a carcinogen.
EFFECTS OF OVEREXPOSURE:
VX is a lethal anticholinergic agent with the median dose in man being: LC50 (skin) = 0.135 mg/kg; ID50 (Skin) - 0.07 - 0.71 mg/kg; LCt50 (inhalation) = 30 mg min/m3; LCt50 (inhalation) - 30 mg min/m3; LCt50 (inhalation) - 24 mg min/m3.
1. One to several minutes after overexposure to airborne VX the following acute symptoms appear:
1. LOCAL EFFECTS (lasting 1-15 days, increases with dose)
1. On eyes: Miosis (constriction of pupils); redness, pressure sensation on eyes.
2. By inhalation: Rhinorrhea (runny nose), nasal congestion, tightness in chest, wheezing, salivation, nausea, vomiting
2. SYSTEMIC EFFECTS (increases with dose): By inhalation - excessive secretion causing coughing/breathing difficulty; salivation and sweating; vomiting, diarrhea; stomach cramps; involuntary urination/defecation; generalized muscle twitching/muscle cramps; CNS depression including anxiety, restlessness, giddiness, insomnia, excessive dreaming and nightmares. With more severe exposure, also headache, tremor, drowsiness, concentration difficulty, memory impairment, confusion, unsteadiness on standing or walking, and progressing to death.
2. After exposure to liquid VX, the following acute symptoms appear:
1. Local Effects:
1. On eyes: Miosis, redness, pressure sensation on eyes.
2. By ingestion: salivation, anorexia, nausea, vomiting, abdominal cramps, diarrhea, involuntary defecation, heartburn.
3. On skin: Sweating, muscle twitching
2. Systemic Effects: Similar to generalized effects from exposure to airborne VX.
3. Chronic overexposure to VX causes forgetfulness, thinking difficulty, vision disturbances, muscular aches/pains. Although cer-organophosphate pesticides have been shown to be teratogenic in animals, these effects have not been documented in carefully controlled toxicological evaluations for VX.
EMERGENCY AND FIRST AID PROCEDURES:
• INHALATION: Hold breath until respiratory protective mask is donned. If severe signs of agent exposure appear (chest tightens, pupil constriction, incoordination, etc.), immediately administer, in rapid succession, all three Nerve Agent Antidote Kit(s), Mark I injectors (or atropine if directed by the local physician). Injections using the Mark I kit injectors may be repeated at 5 to 20 minute intervals if signs and symptoms are progressing until three series of injections have been administered. No more injections will be given unless directed by medical personnel. In addition, a record will be maintained of all injections given. If breathing has stopped, give artificial respiration. Mouth-to-mouth resuscitation should be used when approved mask-bag or oxygen delivery systems are not available. Do not use mouth-to-mouth resuscitation when facial contamination exists. If breathing is difficult, administer oxygen. Seek medical attention IMMEDIATELY.
• EYE CONTACT: IMMEDIATELY flush eyes with water for 10-15 minutes, then don respiratory protective mask. Although miosis (pinpointing of the pupils) may be an early sign of agent exposure, an injection will not be administered when miosis is the only sign present. Instead, the individual will be taken IMMEDIATELY to the medical treatment facility for observation.
• SKIN CONTACT: Don respsiratory protective mask and remove contaminated clothing. Immediately wash contaminated skin with a solution of 5% household bleach. Rinse well with water to remove excess bleach followed by copious soap and water wash. Administer nerve agent antidote kit, Mark I, only if local sweating and muscular twitching symptoms are present. Seek medical attention IMMEDIATELY.
• INGESTION: Do not induce vomiting. First symptoms are likely to be gastronintestinal. IMMEDIATELY administer Nerve Agent Antidote kit, Mark I. Seek medical attention immediately.
Section VI: Reactivity Data
STABILITY: Relatively stable at room temperature. Unstabilized VX of 95% purity decomposed at a rate of 5% a month at 71 deg. C.
HAZARDOUS DECOMPOSITION PRODUCTS:
During basic hydrolysis of VX up to about 10% of the agent is converted to EA2192 (diisopropylaminoethyl methylphosphonothioic acid). Based on the concentration of EA2192 expected to be formed during hydrolysis and its toxicity (1.4 mg/kg dermal in rabbit at 24 hours in a 10/90 wt% ethanol/water solution), a Class B poison would result.
The large scale decon procedure, which uses both HTH and NaOH, destroys VX by oxidation and hydrolysis. Typically the large scale product contains 0.2 - 0.4 wt% EA2192 at 24 hours. At pH 12, the EA2192 in the large scale product has a half-life of about 14 days. Thus the 90 day holding period at pH 12 results in about a 64-fold reduction of EA2192 (six half-lives). This holding period has been shown to be sufficient to reduce the toxicity of the product below that of a Class B poison.
Other less toxic products are ethyl methylphosphonic acid, methylphosphinic acid, diisopropylaminoethyl mercaptan, diethyl methylphosphonate, and ethanol.
The small scale decontamination procedure uses sufficient HTH to oxidize all VX thus no EA2192 is formed.
HAZARDOUS POLYMERIZATION: Will not occur.
Section VII: Spill, Leak and Disposal Procedures
STEPS TO BE TAKEN IN CASE MATERIAL IS RELEASED OR SPILLED: If leak or spills occur, only personnel in full protective clothing (see Section 8) will remain in area. In case of personnel contamination, see Section V "Emergency and First Aid Instructions." Spills must be contained by covering with vermiculite, diatomaceous earth, clay or fine sand. This containment is followed by the following treatment.
RECOMMENDED LABORATORY PROCEDURES (For Quantities less than 50 grams):
If the active chlorine of the Calcium Hypochlorite (HTH) is at least 55 percent, then 80 grams of a 10 percent slurry is required for each gram of VX. Proportionally more HTH is required if the chlorine activity of the HTH is lower than 55 percent. The mixture is agitated as the VX is added and the agitation is maintained for a minimum of one hour. If phasing of the VX/decon solution continues after 5 minutes, an amount of denatured ethanol equal to a 10 wt percent of the total agent/decon shall be added to assist miscibility. NOTE: Ethanol should be minimized to prevent the formation of a hazardous waste.
Upon completion of the one hour agitation the decon mixture shall be adjusted to a pH between 10 and 11. Conduct general area monitoring to confirm that the atmospheric concentrations do not exceed the airborne exposure limit (see Secions 2 and 8).
RECOMMENDED FIELD PROCEDURES (For quantities greater than 50 grams):
NOTE: These procedures can only be used with the approval of the CRDEC Safety Officer.
An alcoholic HTH mixture is prepared by adding 100 milliliters of denatured ethanol to a 900 milliliter slurry of 10 percent HTH in water. This mixture should be made just prior to use since the HTH can react with the ethanol. Fourteen grams of alcoholic HTH solution is used for each gram of VX. Agitate the contaminaton mixture as the VX is added. Continue the agitation for a minimum of one hour. This reaction is reasonable exothermic and evolves substantial off gassing. The evolved reaction gases should be routed through a decontaminate filled scrubber prior to release through filtration systems.
After completion of the one hour minimum agitation, 10 percent Sodium Hydroxide is added in a quantity equal to that necessary to assure that a pH of 12.5 is maintained for a period not less than 24 hours. Hold the material at a pH between 10 ad 12 for a period not less than 90 days to ensure that a hazardous intermediate material is not formed.
After sealing the head, the exterior of the drum shall be decontaminated and then labeled IAW EPA and DOT regulations. All leaking containers shall be overpacked with vermiculite placed between the interior and exterior containers. Decontaminate and label IAW EPA and DOT regulations. Dispose of the material IAW waste disposal methods provided below. Conduct general area monitoring to confirm that the atmospheric concentrations do not exceed the airborne exposure limit (see Section 2 and 8).
If the alcoholic Calcium Hypochlorite (HTH) mixture is not available then the following decontaminants may be used instead and are listed in the order of preference: Decontamination Solution No. 2 (DS2), Supertropical Bleach Slurry (STB), and Sodium Hypochlorite.
WASTE DISPOSAL METHOD: Open pit burning or burying of VX or items containing or contaminated with VX in any quantity is prohibited. The detoxified VX (using procedures above) can be thermally destroyed by incineration in an EPA approved incinerator in accordance with appropriate provisions of Federal, state and local RCRA regulations. NOTE: Some states define decontaminated surety material as a RCRA Hazardous Waste.
Section VIII: Special Protection Informaton
RESPIRATORY PROTECTION:
VX Concentration Respiratory Protective Equipment
Less than 0.00001 mg/m3 M9, M17, or M40 series mask shall be available for escape
as necessary
0.00001 mg/m3 to 0.02 mg/m3 M9, or M40 series mask with Level A or Level B protective
ensemble (see AMCR 385-131 for determination of
appropirate level).
Demilitarization Protective Emsemble (DPE), or
Toxicological Agent Protective Ensemble Self-Contained
(TAPES), used with prior approval from AMC Field Safety
Activity.
Greater than 0.02 mg/m3 or DPE or TAPES used with prior approval from AMC Field
unknown Field Safety Activity
NOTE: When DPE or TAPES is not available the M9 or
M40 series mask with Level A protective ensemble can be
used. However, use time shall be restricted to the extent
operationally feasible, and may not exceed one hour.
As an additional precaution, the cuffs of the sleeves and the
legs of the M3 suit shall be taped to the gloves and boots
respectively to reduce aspiration.
VENTILATION: Local Exhaust: Must be filtered or scrubbed to limit exit conc.to <.00001 mg/m3.
Special: Chemical laboratory hoods shall have an average inward face velocity of 100 linear feet per minute (lfpm) + 10 percent with the velocity at any point not deviating from the average face velocity by more than 20 percent. Laboratory hoods shall be located such that cross-drafts do not exceed 20 percent of the inward face velocity. A visual performance test utilizing smoke- producing devices shall be performed in assessing the ability of the hood to contain agent VX.
Emergency back-up power necessary. Hoods should be tested semi-annually or after modification or maintenance operations. Operations should be performed 20 cm inside hood face.
Other: Recirculation of exhaust air from agent areas is prohibited. No connection between agent areas and other areas through ventilation system is permitted.
PROTECTIVE GLOVES: Butyl Glove M3 and M4; Northon, Chemical Protective Glove Set
EYE PROTECTION: Chemical Goggles. For splash hazards use goggles and faceshield.
OTHER PROTECTIVE EQUIPMENT:
Full protective clothing will consist of M9 mask and hood, m3 butyl rubber suit (M3), M2A1 butyl boots, M3 and M4 gloves, unimpregnated underwear, or demilitarization protective ensemble (DPE). For laboratory operations, wear lab coats and have a protective mask readily available.
In addition, daily clean smock, foot covers, and head covers will be required when handling contaminated lab animals.
MONITORING: Available monitoring equipment for agent HD is the M8/M9 Detector paper, ACADA), detector ticket, M256/M256A1 kits, bubbler. Depot Area Air Monitoring System (DAMMS), Automated Continuous Air Monitoring System (ACMS), Real-Time Monitor (RTM), Demilitarization Chemical Agent Concentrator (DCAC), M8/M43, M8A1/M43A1, CAM-M1, Hydrogen Flame Photometric Emission Detector (HYFED), and the Minature Chemical Agent Monitor (MINICAM).
Section IX: Special Precautions
PRECAUTIONS TO BE TAKEN IN HANDLING AND STORING: In handling, the buddy system will be incorporated. No smoking, eating or drinking in areas containing agent is permitted. Containers should be periodically inspected for leaks (either visually or by a detector kit). Stringent control over all personnel practices must be exercised. Decontamination equipment shall be conveniently located. Exits must be designed to permit rapid evacuation. Chemical showers, eyewash stations, and personal cleanliness facilities shall be provided. Wash hands before meals and each worker will shower thoroughly with special attention given to hair, face, neck, and hands, using plenty of soap before leaving at the end of the workday.
OTHER PRECAUTIONS: Agent must be double-contained in liquid and vapor-tight containers when in storage or when outside of the ventilation hood.
For additional information, see AMC-R 385-131, "Safety Regulations for Chemical Agents H, HD, HT, GB, and VX" and USAEHA Technical Guide No. 169, "Occupational Health Guidelines for the Evaluation and Control of Occupational Exposure to Nerve Agents GA, GB, GD, and VX."
Section X: Transportation Data
PROPER SHIPPING NAME: Poisonous liquid, n.o.s.
DOT HAZARD CLASSIFICATION: Poison A
DOT LABEL: Poison gas
DOT MARKING: Poisonous liquid, n.o.s. (O-ethyl S-(2-diisopropylaminoothyl) methyl phosphonothioate) NA 1955
DOT PLACARD: POISON GAS
EMERGENCY ACCIDENT PRECAUTIONS AND PROCEDURES: See Section IV, VII and VIII.
PRECAUTIONS TO BE TAKEN IN TRANSPORTATION:
Motor vehicles will be placarded regardless of quantity. Driver shall be given full and complete information regarding shipment and conditions in case of emergency. AR 50-6 deals specifically with the shipment of chemical agents. Shipments of agent will be escorted in accordance with AR 740-32.
While the Chemical Research Development and Engineering Center, Department of the Army believes that the data contained herein are factual and the opinions expressed are those of qualified experts regarding the results of the tests conducted, the data are not to be taken as a warranty or representation for which the Department of the Army or Chemical Research Development Engineering Center assumes legal responsibility. They are offered solely for your consideration, investigation, and verification. Any use of these data and information must be determined by the user to be in accordance with applicable Federal, State, and local laws and regulations.
Addendum A: Physiological Effects
ACUTE PHYSIOLOGICAL EFFECTS:
Site of Action Signs and Symptoms
Following Local Exposure
Muscarine-like-
Pupils Miosis, marked, usually maximal (pinpoint),
sometimes unequal.
Ciliary body Frontal headache, eye pain on focusing, slight
dimness of vision, occasional nausea and vomiting.
Conjunctivae Hyperemia
Nasal mucous membranes Rhinorrhea, hyperemia
Bronchial tree Tightness in chest, sometimes with prolonged
wheezing expiration suggestive of broncho-
constriction or increased secretion, cough..
Following Systemic Absorption
Bronchial tree Tightness in chest, with prolonged wheezing,
expiration suggestive of broncho-constricion or
increased secretion, dyspnea, slight pain in chest,
increased bronchial secretion, cough, pulmonary
edema, cyanosis.
Gastrointestinal Anorexia, nausea, vomiting, abdominal cramps,
epigastric and substernal tightness (cardiospasm)
with "heartburn" and eructation, diarrhea, tenesmus,
involuntary defecation.
Sweat glands Increased sweating
Salivary glands Increased salivation
Lacrimal glands Increased lacrimation
Heart Slight bradycardia
Pupils Slight miosis, occasionally unequal, later maximal
miosis (pinpoint).
Ciliary body Blurring of vision
Bladder Frequent, involuntary micturition
Nicotine-like
Striated muscle Easy fatigue, mild weakness, muscular twitching,
fasciculations, cramps, generalized weakness,
including muscles of respiration, with dyspnea and
cyanosis.
Sympathetic ganglia Pallor, occasional elevation of blood pressure.
Central Nervous system Giddiness, tension, anxiety, jitteriness, restlessness,
emotional lability, excessive dreaming, insomnia,
nightmares, headaches, tremor, withdrawal and
depression, bursts of slow waves of elevated
voltage in EEG, especially on over-ventilation,
drowsiness, difficult concentration, slowness on
recall, confusion, slurred speech, ataxia,
generalized weakness, coma, with absence of
reflexes, Cheyne-Stokes respirations, convulsions,
depression of respiratory and circulatory centers,
with dyspnea, cyanosis, and fall in blood pressure.
CHRONIC PHYSIOLOGICAL EFFECTS:
Acute Exposure
• If recovery from nerve agent poisoning occurs, it will be complete unless anoxia or convulsions have gone unchecked so long that irreversible central nervous system changes due to anoxemia have occurred.
Chronic Exposure
• The inhibition of cholinesterase enzymes throughout the body by nerve agents is more or less irreversible so that their effects are prolonged. Until the tissue cholinesterase enzymes are restored to normal activity, probably by very slow regeneration over a period of weeks or 2 to 3 months if damage is severe there is a period of increased susceptibility to the effects of another exposure to any nerve agent. During this period the effects of repeated exposures are cumulative; after a single exposure, daily exposure to concentrations of a nerve agent insufficient to product symptoms may result in the onset of symptoms after several days.
• Continued daily exposure may be followed by increasingly severe effects. After symptoms subside, increased susceptibility persists for one to several days. The degree of exposure required to produce recurrence of symptoms, and the severity of these symptoms, depend on duration of exposure and time intervals between exposures. Increased susceptibility is not limited to the particular nerve agent initially absorbed.
• Estimates have been made for the times as which 50% of exposed subjects would be affected (Et50's) at median incapacitating doses. These are presented below:
____________________________________________________________________________
Et50 Degree of ICt50 Exposure Time
Effectiveness
______________________________________________________________________________
min mg min/m3 min
1.5 Moderate 27 0.5
3.0 Incap. 27 2.0
6.0 40 10.0
1.0 Severe 37 0.5
3.8 Incap. 37 2.0
7.8 56 10.0
2.0 Very 47 0.5
4.5 Severe 47 2.0
9.5 Incap. 72 10.0
6.5 Death 70 5.0
9.0 70 2.0
13.5 103 10.0
______________________________________________________________________________
Exposure to high concentrations of nerve agent may bring on incoordination, mental confusion
and collapse so rapidly that the casualty cannot perform self-aid. If this happens, the man
nearest to him will give first aid.
Onset Time of Symptoms
______________________________________________________________________________
When Effects
Types of Route of Description Appear After
Effects Absorption of Effects Exposure
______________________________________________________________________________
Vapor Lungs Rhinorrhea, nasal Hyperemia One to several minutes
Local tightness in chest, wheezing
Vapor Eyes Miosis, conjectival hyperemia One to several minutes
Local eye pain, frontal headache
Vapor Lungs or Muscarine-like, nicotine-like Less than 1 min. to a few
min.
Systemic eyes and central nervous system after moderate or marked
effects. (See 2a above) exposure: about 30 min. after
mild exposure
Liquid Eyes Same as vapor effects Instantly
Local
Liquid Ingestion Gastrointestinal. (See 2a above). About 30 min. after ingestion
Local
Liquid Skin Local sweating and muscular 3 min to 2 hours
Local twitching
Liquid Lungs See 2a above Several minutes
Sytemic
Liquid Eyes Same as for vapor Several minutes
Systemic
Liquid Skin Generalized sweating 15 minutes to 2 hours
Systemic
Liquid Ingestion Gastrointestinal (see 2a above) 15 minutes to 2 hours
Systemic
Onset Time of Symptoms. (cont'd)
______________________________________________________________________________
Duration of Effects After
______________________________________________________________________________
Types of Route of Mild Severe
Effects Absorption Exposure Exposure
______________________________________________________________________________
Vapor Lungs A few hours 1 to 2 days
Local
Vapor Eyes Miosis - 3 to 14 days
Local 24 hours 2 to 5 days
Vapor Lungs or eyes Several hours 8 days
Systemic
Liquid Eyes Similar to effects
Local of vapor
Liquid Ingestion 3 days 5 days
Local
Liquid Skin 3 days 5 days
Local
Liquid Lungs 1 to 5 days
Systemic
Liquid Eyes 2 to 4 days
Systemic
Liquid Skin 2 to 5 days
Systemic
Liquid Ingestion 3 to 5 days
Systemic
Addendum B: First Aid Procedures
1. Exposed personnel will be removed immediately to an uncontaminated atmosphere. Personnel handling casualty cases will give consideration to their own safety and will take precautions and employ the prerequisite protective equipment to avoid becoming exposed themselves.
CAUTION: Due to the rapid effects of nerve agents, it is extremely important that decontamination of personnel not be delayed by attempting to blot off excessive agent prior to decontamination with sodium hypochlorite.
2. The causalty will then be decontaminated by immediately removing any contaminated clothing and washing the contaminated areas with copious amounts of soap and water, 5% sodium hypochlorite solution, or liquid household bleach (nominal 5% solution sodium hypochlorite) and flushing with clean water. Mask will be left on the victim until decontamination has been completed unless it has been determined that areas of the face were contaminated and the mask must be removed to facilitate decontamination. After decontamination, the contaminated clothing will be removed and skin contamination washed away. If possible, decontamination will be completed before the casualty is taken to the aid station of medical facility.
CAUTION: Care must be taken when decontaminating facial areas to avoid getting the hypochlorite into the eye or mouth. Only clean water shall be used when flushing the eyes or mouth. Skin surfaces decontaminated with bleach should be thoroughly flushed with water to prevent skin irritation from the bleach.
3. If there is no apparent breathing, artifical resuscitation will be started immediately (mouth-to-mouth, or with mechanical resuscitator). The situation will dictate method of choice, e.g., contaminated face. Do not use mouth-to-mouth resuscitation when facial contamination exists. When appropriate and trained personnel are available, cardiopulmonary resuscitation (CPR) may be necessary.
4. An individual who has received a known agent exposure or who exhibits definite signs or symptoms of agent exposure shall be injected immediately with the Nerve Agent Antidote Kit, MARK I.
1. Some of the early symptoms of a vapor exposure may be rhinorrhea (runny nose) and/or tightness in the chest with shortness of breath (bronchial construction).
2. Some of the early symptoms of a percutaneous exposure may be local muscular twitching or sweating at the area of exposure followed by nausea or vomiting.
3. Although myosis (pin-pointing of the pupils) may be an early sign of agent exposure, a Mark I Kit shall not be administered when myosis is the only sign present. Instead, the individual shall be taken immediately to the medical facility for observation.
4. Injections using the MARK I kit injectors (or atropine only if directed by the local physician) may be repeated at 5 to 20 minute intervals if signs and symptoms are progressing until three series of injections have been administered. No more injections will be given unless directed by medical personnel. In addition, a record will maintained of all injections given.
5. Administer, in rapid succession, all three MARK I kit injectors (or atropine if directed by the local physician) in the case of SEVERE signs of agent exposure.
CAUTION: The nerve Agent Antidote Kit, MARK I does not act as a prophylactic and shall not be administered until an agent exposure has been ascertained.
5. If indicated, CPR should be started immediately. Mouth-to-mouth resuscitation should be used when approved mask-bag or oxygen delivery systems are not available. Do not use mouth-to-mouth resuscitation when facial contamination exists.
Section I: General Information
MANUFACTURER'S NAME: Department of the Army
MANUFACTURER'S ADDRESS:
U.S. Army Armament, Munitions and Chemical Command
Chemical Research, Development and Engineering Center
ATTN: SMCCR-CMS-E
Aberdeen Proving Ground, MD 21010-5423
CAS REGISTRY NUMBER: 50782-69-9, 51848-47-6, 53800-40-1, 70938-84-0
CHEMICAL NAME: Phosphonothioic acid, methyl-, S-(2bis(1-methylethylamino)ethyl) 0-ethyl ester
ALTERNATE CHEMICAL NAMES:
• O-ethyl S-(2-diisopropylaminoethyl) methylphosphonothioate
• S-2-Diisopropylaminoethyl O-ethyl methylphosphonothioate
• S-2 (2-Diisopropylamino)ethyl) O-ethyl methylphosphonothiolate
• O-ethyl S-(2-diisoproplyaminoethy) methylphosphonothioate
• O-ethyl S-(2-diisoproplyaminoethy) methylthiolphosphonoate
TRADE NAME AND SYNONYMS:
• VS
• EA 1701
• TX60
CHEMICAL FAMILY: Sulfinated organophosphorus compound
FORMULA: C11 H26 N 02 P S
NFPA 704 SIGNAL:
• Health - 4
• Flammability - 1
• Reactivity - 1
Section II: Composition
INGREDIENTS FORMULA PERCENTAGE AIRBORNE
NAME BY WEIGHT EXPOSURE LIMIT
VX C11H26N02PS 100 .00001 mg/m3
Section III: Physical Data
BOILING POINT DEG F (DEG C): 568 (298)
VAPOR PRESSURE (mm Hg): 0.0007 @ 25 DEG C
VAPOR DENSITY (AIR=1): 9.2
SOLUBILITY IN WATER: Moderate
APPEARANCE AND ODOR: Colorless to straw colored liquid & odorless, similar in appearance to motor oil.
Section IV: Fire and Explosion Data
FLASHPOINT: 159 DEG C (McCutchan-Young)
FLAMMABILITY LIMITS: (% by volume): Not available
LOWER EXPLOSIVE LIMIT: Not applicable
UPPER EXPLOSIVE LIMIT: Not applicable
EXTINGUISING MEDIA: Water mist, fog, foam, CO2 - Avoid using extinguishing methods that will cause splashing or spreading of the VX.
SPECIAL FIRE FIGHTING PROCEDURES:
All persons not engaged in extinguishing the fire should be immediately evacuated from the area. Fires involving VX should be contained to prevent contamination to uncontrolled areas. When responding to a fire alarm in buildings or areas containing agents, firefighting personnel should wear full firefighter protective clothing (without TAP clothing) during chemical agent firefighting and fire rescue operations.
Respiratory protection is required. Positive pressure, full facepiece, NIOSH-approved self contained breathing apparatus (SCBA) will be worn where there is danger of oxygen deficiency and when directed by the fire chief of chemical accident/incident (CAI) operations officer. The M9 or M17 series mask may be worn in lieu of SCBA when there is no danger of oxygen deficiency. In cases where firefighters are responding to a chemical accident/incident for rescue/reconnaissance purposes vice firefighting, they will wear appropriate levels of protective clothing (see Section 8).
Do not breathe fumes. Skin contact with V-agents must be avoided at all times. Although the fire may destroy most of the agent, care must still be taken to assure the agent or contaminated liquids do not further contaminate other areas or sewers. Contact with VX or VX vapors can be fatal.
UNUSUAL FIRE AND EXPLOSION HAZARDS: None known.
Section V: Health Hazard Data
RECOMMENDED EXPOSURE LIMIT (REL):
The suggested permissible airborne exposure concentration of VX for an 8 hour workday or a 40 hour work week is an 8 hour time weighted average (TWA) of 0.00001 mg/m3 (9 x 10-7 ppm). This value is based on the TWA of VX as proposed in the USAEHA Technical Guide No. 169, "Occupational Health Guidelines for the Evaluation and Control of Occupational Exposure to Nerve Agents GA, GB, GD, and VX." To date, however, the Occupational Safety and Health Administration (OSHA) has not promulgated permissible exposure concentration for VX.
VX is not listed by the International Agency for Research on Cancer (IARC), American Conference of Governmental Industrial Hygienists (ACGIH), Occupational Safety and Health Administration (OSHA), or National Toxicology Program (NTP) as a carcinogen.
EFFECTS OF OVEREXPOSURE:
VX is a lethal anticholinergic agent with the median dose in man being: LC50 (skin) = 0.135 mg/kg; ID50 (Skin) - 0.07 - 0.71 mg/kg; LCt50 (inhalation) = 30 mg min/m3; LCt50 (inhalation) - 30 mg min/m3; LCt50 (inhalation) - 24 mg min/m3.
1. One to several minutes after overexposure to airborne VX the following acute symptoms appear:
1. LOCAL EFFECTS (lasting 1-15 days, increases with dose)
1. On eyes: Miosis (constriction of pupils); redness, pressure sensation on eyes.
2. By inhalation: Rhinorrhea (runny nose), nasal congestion, tightness in chest, wheezing, salivation, nausea, vomiting
2. SYSTEMIC EFFECTS (increases with dose): By inhalation - excessive secretion causing coughing/breathing difficulty; salivation and sweating; vomiting, diarrhea; stomach cramps; involuntary urination/defecation; generalized muscle twitching/muscle cramps; CNS depression including anxiety, restlessness, giddiness, insomnia, excessive dreaming and nightmares. With more severe exposure, also headache, tremor, drowsiness, concentration difficulty, memory impairment, confusion, unsteadiness on standing or walking, and progressing to death.
2. After exposure to liquid VX, the following acute symptoms appear:
1. Local Effects:
1. On eyes: Miosis, redness, pressure sensation on eyes.
2. By ingestion: salivation, anorexia, nausea, vomiting, abdominal cramps, diarrhea, involuntary defecation, heartburn.
3. On skin: Sweating, muscle twitching
2. Systemic Effects: Similar to generalized effects from exposure to airborne VX.
3. Chronic overexposure to VX causes forgetfulness, thinking difficulty, vision disturbances, muscular aches/pains. Although cer-organophosphate pesticides have been shown to be teratogenic in animals, these effects have not been documented in carefully controlled toxicological evaluations for VX.
EMERGENCY AND FIRST AID PROCEDURES:
• INHALATION: Hold breath until respiratory protective mask is donned. If severe signs of agent exposure appear (chest tightens, pupil constriction, incoordination, etc.), immediately administer, in rapid succession, all three Nerve Agent Antidote Kit(s), Mark I injectors (or atropine if directed by the local physician). Injections using the Mark I kit injectors may be repeated at 5 to 20 minute intervals if signs and symptoms are progressing until three series of injections have been administered. No more injections will be given unless directed by medical personnel. In addition, a record will be maintained of all injections given. If breathing has stopped, give artificial respiration. Mouth-to-mouth resuscitation should be used when approved mask-bag or oxygen delivery systems are not available. Do not use mouth-to-mouth resuscitation when facial contamination exists. If breathing is difficult, administer oxygen. Seek medical attention IMMEDIATELY.
• EYE CONTACT: IMMEDIATELY flush eyes with water for 10-15 minutes, then don respiratory protective mask. Although miosis (pinpointing of the pupils) may be an early sign of agent exposure, an injection will not be administered when miosis is the only sign present. Instead, the individual will be taken IMMEDIATELY to the medical treatment facility for observation.
• SKIN CONTACT: Don respsiratory protective mask and remove contaminated clothing. Immediately wash contaminated skin with a solution of 5% household bleach. Rinse well with water to remove excess bleach followed by copious soap and water wash. Administer nerve agent antidote kit, Mark I, only if local sweating and muscular twitching symptoms are present. Seek medical attention IMMEDIATELY.
• INGESTION: Do not induce vomiting. First symptoms are likely to be gastronintestinal. IMMEDIATELY administer Nerve Agent Antidote kit, Mark I. Seek medical attention immediately.
Section VI: Reactivity Data
STABILITY: Relatively stable at room temperature. Unstabilized VX of 95% purity decomposed at a rate of 5% a month at 71 deg. C.
HAZARDOUS DECOMPOSITION PRODUCTS:
During basic hydrolysis of VX up to about 10% of the agent is converted to EA2192 (diisopropylaminoethyl methylphosphonothioic acid). Based on the concentration of EA2192 expected to be formed during hydrolysis and its toxicity (1.4 mg/kg dermal in rabbit at 24 hours in a 10/90 wt% ethanol/water solution), a Class B poison would result.
The large scale decon procedure, which uses both HTH and NaOH, destroys VX by oxidation and hydrolysis. Typically the large scale product contains 0.2 - 0.4 wt% EA2192 at 24 hours. At pH 12, the EA2192 in the large scale product has a half-life of about 14 days. Thus the 90 day holding period at pH 12 results in about a 64-fold reduction of EA2192 (six half-lives). This holding period has been shown to be sufficient to reduce the toxicity of the product below that of a Class B poison.
Other less toxic products are ethyl methylphosphonic acid, methylphosphinic acid, diisopropylaminoethyl mercaptan, diethyl methylphosphonate, and ethanol.
The small scale decontamination procedure uses sufficient HTH to oxidize all VX thus no EA2192 is formed.
HAZARDOUS POLYMERIZATION: Will not occur.
Section VII: Spill, Leak and Disposal Procedures
STEPS TO BE TAKEN IN CASE MATERIAL IS RELEASED OR SPILLED: If leak or spills occur, only personnel in full protective clothing (see Section 8) will remain in area. In case of personnel contamination, see Section V "Emergency and First Aid Instructions." Spills must be contained by covering with vermiculite, diatomaceous earth, clay or fine sand. This containment is followed by the following treatment.
RECOMMENDED LABORATORY PROCEDURES (For Quantities less than 50 grams):
If the active chlorine of the Calcium Hypochlorite (HTH) is at least 55 percent, then 80 grams of a 10 percent slurry is required for each gram of VX. Proportionally more HTH is required if the chlorine activity of the HTH is lower than 55 percent. The mixture is agitated as the VX is added and the agitation is maintained for a minimum of one hour. If phasing of the VX/decon solution continues after 5 minutes, an amount of denatured ethanol equal to a 10 wt percent of the total agent/decon shall be added to assist miscibility. NOTE: Ethanol should be minimized to prevent the formation of a hazardous waste.
Upon completion of the one hour agitation the decon mixture shall be adjusted to a pH between 10 and 11. Conduct general area monitoring to confirm that the atmospheric concentrations do not exceed the airborne exposure limit (see Secions 2 and 8).
RECOMMENDED FIELD PROCEDURES (For quantities greater than 50 grams):
NOTE: These procedures can only be used with the approval of the CRDEC Safety Officer.
An alcoholic HTH mixture is prepared by adding 100 milliliters of denatured ethanol to a 900 milliliter slurry of 10 percent HTH in water. This mixture should be made just prior to use since the HTH can react with the ethanol. Fourteen grams of alcoholic HTH solution is used for each gram of VX. Agitate the contaminaton mixture as the VX is added. Continue the agitation for a minimum of one hour. This reaction is reasonable exothermic and evolves substantial off gassing. The evolved reaction gases should be routed through a decontaminate filled scrubber prior to release through filtration systems.
After completion of the one hour minimum agitation, 10 percent Sodium Hydroxide is added in a quantity equal to that necessary to assure that a pH of 12.5 is maintained for a period not less than 24 hours. Hold the material at a pH between 10 ad 12 for a period not less than 90 days to ensure that a hazardous intermediate material is not formed.
After sealing the head, the exterior of the drum shall be decontaminated and then labeled IAW EPA and DOT regulations. All leaking containers shall be overpacked with vermiculite placed between the interior and exterior containers. Decontaminate and label IAW EPA and DOT regulations. Dispose of the material IAW waste disposal methods provided below. Conduct general area monitoring to confirm that the atmospheric concentrations do not exceed the airborne exposure limit (see Section 2 and 8).
If the alcoholic Calcium Hypochlorite (HTH) mixture is not available then the following decontaminants may be used instead and are listed in the order of preference: Decontamination Solution No. 2 (DS2), Supertropical Bleach Slurry (STB), and Sodium Hypochlorite.
WASTE DISPOSAL METHOD: Open pit burning or burying of VX or items containing or contaminated with VX in any quantity is prohibited. The detoxified VX (using procedures above) can be thermally destroyed by incineration in an EPA approved incinerator in accordance with appropriate provisions of Federal, state and local RCRA regulations. NOTE: Some states define decontaminated surety material as a RCRA Hazardous Waste.
Section VIII: Special Protection Informaton
RESPIRATORY PROTECTION:
VX Concentration Respiratory Protective Equipment
Less than 0.00001 mg/m3 M9, M17, or M40 series mask shall be available for escape
as necessary
0.00001 mg/m3 to 0.02 mg/m3 M9, or M40 series mask with Level A or Level B protective
ensemble (see AMCR 385-131 for determination of
appropirate level).
Demilitarization Protective Emsemble (DPE), or
Toxicological Agent Protective Ensemble Self-Contained
(TAPES), used with prior approval from AMC Field Safety
Activity.
Greater than 0.02 mg/m3 or DPE or TAPES used with prior approval from AMC Field
unknown Field Safety Activity
NOTE: When DPE or TAPES is not available the M9 or
M40 series mask with Level A protective ensemble can be
used. However, use time shall be restricted to the extent
operationally feasible, and may not exceed one hour.
As an additional precaution, the cuffs of the sleeves and the
legs of the M3 suit shall be taped to the gloves and boots
respectively to reduce aspiration.
VENTILATION: Local Exhaust: Must be filtered or scrubbed to limit exit conc.to <.00001 mg/m3.
Special: Chemical laboratory hoods shall have an average inward face velocity of 100 linear feet per minute (lfpm) + 10 percent with the velocity at any point not deviating from the average face velocity by more than 20 percent. Laboratory hoods shall be located such that cross-drafts do not exceed 20 percent of the inward face velocity. A visual performance test utilizing smoke- producing devices shall be performed in assessing the ability of the hood to contain agent VX.
Emergency back-up power necessary. Hoods should be tested semi-annually or after modification or maintenance operations. Operations should be performed 20 cm inside hood face.
Other: Recirculation of exhaust air from agent areas is prohibited. No connection between agent areas and other areas through ventilation system is permitted.
PROTECTIVE GLOVES: Butyl Glove M3 and M4; Northon, Chemical Protective Glove Set
EYE PROTECTION: Chemical Goggles. For splash hazards use goggles and faceshield.
OTHER PROTECTIVE EQUIPMENT:
Full protective clothing will consist of M9 mask and hood, m3 butyl rubber suit (M3), M2A1 butyl boots, M3 and M4 gloves, unimpregnated underwear, or demilitarization protective ensemble (DPE). For laboratory operations, wear lab coats and have a protective mask readily available.
In addition, daily clean smock, foot covers, and head covers will be required when handling contaminated lab animals.
MONITORING: Available monitoring equipment for agent HD is the M8/M9 Detector paper, ACADA), detector ticket, M256/M256A1 kits, bubbler. Depot Area Air Monitoring System (DAMMS), Automated Continuous Air Monitoring System (ACMS), Real-Time Monitor (RTM), Demilitarization Chemical Agent Concentrator (DCAC), M8/M43, M8A1/M43A1, CAM-M1, Hydrogen Flame Photometric Emission Detector (HYFED), and the Minature Chemical Agent Monitor (MINICAM).
Section IX: Special Precautions
PRECAUTIONS TO BE TAKEN IN HANDLING AND STORING: In handling, the buddy system will be incorporated. No smoking, eating or drinking in areas containing agent is permitted. Containers should be periodically inspected for leaks (either visually or by a detector kit). Stringent control over all personnel practices must be exercised. Decontamination equipment shall be conveniently located. Exits must be designed to permit rapid evacuation. Chemical showers, eyewash stations, and personal cleanliness facilities shall be provided. Wash hands before meals and each worker will shower thoroughly with special attention given to hair, face, neck, and hands, using plenty of soap before leaving at the end of the workday.
OTHER PRECAUTIONS: Agent must be double-contained in liquid and vapor-tight containers when in storage or when outside of the ventilation hood.
For additional information, see AMC-R 385-131, "Safety Regulations for Chemical Agents H, HD, HT, GB, and VX" and USAEHA Technical Guide No. 169, "Occupational Health Guidelines for the Evaluation and Control of Occupational Exposure to Nerve Agents GA, GB, GD, and VX."
Section X: Transportation Data
PROPER SHIPPING NAME: Poisonous liquid, n.o.s.
DOT HAZARD CLASSIFICATION: Poison A
DOT LABEL: Poison gas
DOT MARKING: Poisonous liquid, n.o.s. (O-ethyl S-(2-diisopropylaminoothyl) methyl phosphonothioate) NA 1955
DOT PLACARD: POISON GAS
EMERGENCY ACCIDENT PRECAUTIONS AND PROCEDURES: See Section IV, VII and VIII.
PRECAUTIONS TO BE TAKEN IN TRANSPORTATION:
Motor vehicles will be placarded regardless of quantity. Driver shall be given full and complete information regarding shipment and conditions in case of emergency. AR 50-6 deals specifically with the shipment of chemical agents. Shipments of agent will be escorted in accordance with AR 740-32.
While the Chemical Research Development and Engineering Center, Department of the Army believes that the data contained herein are factual and the opinions expressed are those of qualified experts regarding the results of the tests conducted, the data are not to be taken as a warranty or representation for which the Department of the Army or Chemical Research Development Engineering Center assumes legal responsibility. They are offered solely for your consideration, investigation, and verification. Any use of these data and information must be determined by the user to be in accordance with applicable Federal, State, and local laws and regulations.
Addendum A: Physiological Effects
ACUTE PHYSIOLOGICAL EFFECTS:
Site of Action Signs and Symptoms
Following Local Exposure
Muscarine-like-
Pupils Miosis, marked, usually maximal (pinpoint),
sometimes unequal.
Ciliary body Frontal headache, eye pain on focusing, slight
dimness of vision, occasional nausea and vomiting.
Conjunctivae Hyperemia
Nasal mucous membranes Rhinorrhea, hyperemia
Bronchial tree Tightness in chest, sometimes with prolonged
wheezing expiration suggestive of broncho-
constriction or increased secretion, cough..
Following Systemic Absorption
Bronchial tree Tightness in chest, with prolonged wheezing,
expiration suggestive of broncho-constricion or
increased secretion, dyspnea, slight pain in chest,
increased bronchial secretion, cough, pulmonary
edema, cyanosis.
Gastrointestinal Anorexia, nausea, vomiting, abdominal cramps,
epigastric and substernal tightness (cardiospasm)
with "heartburn" and eructation, diarrhea, tenesmus,
involuntary defecation.
Sweat glands Increased sweating
Salivary glands Increased salivation
Lacrimal glands Increased lacrimation
Heart Slight bradycardia
Pupils Slight miosis, occasionally unequal, later maximal
miosis (pinpoint).
Ciliary body Blurring of vision
Bladder Frequent, involuntary micturition
Nicotine-like
Striated muscle Easy fatigue, mild weakness, muscular twitching,
fasciculations, cramps, generalized weakness,
including muscles of respiration, with dyspnea and
cyanosis.
Sympathetic ganglia Pallor, occasional elevation of blood pressure.
Central Nervous system Giddiness, tension, anxiety, jitteriness, restlessness,
emotional lability, excessive dreaming, insomnia,
nightmares, headaches, tremor, withdrawal and
depression, bursts of slow waves of elevated
voltage in EEG, especially on over-ventilation,
drowsiness, difficult concentration, slowness on
recall, confusion, slurred speech, ataxia,
generalized weakness, coma, with absence of
reflexes, Cheyne-Stokes respirations, convulsions,
depression of respiratory and circulatory centers,
with dyspnea, cyanosis, and fall in blood pressure.
CHRONIC PHYSIOLOGICAL EFFECTS:
Acute Exposure
• If recovery from nerve agent poisoning occurs, it will be complete unless anoxia or convulsions have gone unchecked so long that irreversible central nervous system changes due to anoxemia have occurred.
Chronic Exposure
• The inhibition of cholinesterase enzymes throughout the body by nerve agents is more or less irreversible so that their effects are prolonged. Until the tissue cholinesterase enzymes are restored to normal activity, probably by very slow regeneration over a period of weeks or 2 to 3 months if damage is severe there is a period of increased susceptibility to the effects of another exposure to any nerve agent. During this period the effects of repeated exposures are cumulative; after a single exposure, daily exposure to concentrations of a nerve agent insufficient to product symptoms may result in the onset of symptoms after several days.
• Continued daily exposure may be followed by increasingly severe effects. After symptoms subside, increased susceptibility persists for one to several days. The degree of exposure required to produce recurrence of symptoms, and the severity of these symptoms, depend on duration of exposure and time intervals between exposures. Increased susceptibility is not limited to the particular nerve agent initially absorbed.
• Estimates have been made for the times as which 50% of exposed subjects would be affected (Et50's) at median incapacitating doses. These are presented below:
____________________________________________________________________________
Et50 Degree of ICt50 Exposure Time
Effectiveness
______________________________________________________________________________
min mg min/m3 min
1.5 Moderate 27 0.5
3.0 Incap. 27 2.0
6.0 40 10.0
1.0 Severe 37 0.5
3.8 Incap. 37 2.0
7.8 56 10.0
2.0 Very 47 0.5
4.5 Severe 47 2.0
9.5 Incap. 72 10.0
6.5 Death 70 5.0
9.0 70 2.0
13.5 103 10.0
______________________________________________________________________________
Exposure to high concentrations of nerve agent may bring on incoordination, mental confusion
and collapse so rapidly that the casualty cannot perform self-aid. If this happens, the man
nearest to him will give first aid.
Onset Time of Symptoms
______________________________________________________________________________
When Effects
Types of Route of Description Appear After
Effects Absorption of Effects Exposure
______________________________________________________________________________
Vapor Lungs Rhinorrhea, nasal Hyperemia One to several minutes
Local tightness in chest, wheezing
Vapor Eyes Miosis, conjectival hyperemia One to several minutes
Local eye pain, frontal headache
Vapor Lungs or Muscarine-like, nicotine-like Less than 1 min. to a few
min.
Systemic eyes and central nervous system after moderate or marked
effects. (See 2a above) exposure: about 30 min. after
mild exposure
Liquid Eyes Same as vapor effects Instantly
Local
Liquid Ingestion Gastrointestinal. (See 2a above). About 30 min. after ingestion
Local
Liquid Skin Local sweating and muscular 3 min to 2 hours
Local twitching
Liquid Lungs See 2a above Several minutes
Sytemic
Liquid Eyes Same as for vapor Several minutes
Systemic
Liquid Skin Generalized sweating 15 minutes to 2 hours
Systemic
Liquid Ingestion Gastrointestinal (see 2a above) 15 minutes to 2 hours
Systemic
Onset Time of Symptoms. (cont'd)
______________________________________________________________________________
Duration of Effects After
______________________________________________________________________________
Types of Route of Mild Severe
Effects Absorption Exposure Exposure
______________________________________________________________________________
Vapor Lungs A few hours 1 to 2 days
Local
Vapor Eyes Miosis - 3 to 14 days
Local 24 hours 2 to 5 days
Vapor Lungs or eyes Several hours 8 days
Systemic
Liquid Eyes Similar to effects
Local of vapor
Liquid Ingestion 3 days 5 days
Local
Liquid Skin 3 days 5 days
Local
Liquid Lungs 1 to 5 days
Systemic
Liquid Eyes 2 to 4 days
Systemic
Liquid Skin 2 to 5 days
Systemic
Liquid Ingestion 3 to 5 days
Systemic
Addendum B: First Aid Procedures
1. Exposed personnel will be removed immediately to an uncontaminated atmosphere. Personnel handling casualty cases will give consideration to their own safety and will take precautions and employ the prerequisite protective equipment to avoid becoming exposed themselves.
CAUTION: Due to the rapid effects of nerve agents, it is extremely important that decontamination of personnel not be delayed by attempting to blot off excessive agent prior to decontamination with sodium hypochlorite.
2. The causalty will then be decontaminated by immediately removing any contaminated clothing and washing the contaminated areas with copious amounts of soap and water, 5% sodium hypochlorite solution, or liquid household bleach (nominal 5% solution sodium hypochlorite) and flushing with clean water. Mask will be left on the victim until decontamination has been completed unless it has been determined that areas of the face were contaminated and the mask must be removed to facilitate decontamination. After decontamination, the contaminated clothing will be removed and skin contamination washed away. If possible, decontamination will be completed before the casualty is taken to the aid station of medical facility.
CAUTION: Care must be taken when decontaminating facial areas to avoid getting the hypochlorite into the eye or mouth. Only clean water shall be used when flushing the eyes or mouth. Skin surfaces decontaminated with bleach should be thoroughly flushed with water to prevent skin irritation from the bleach.
3. If there is no apparent breathing, artifical resuscitation will be started immediately (mouth-to-mouth, or with mechanical resuscitator). The situation will dictate method of choice, e.g., contaminated face. Do not use mouth-to-mouth resuscitation when facial contamination exists. When appropriate and trained personnel are available, cardiopulmonary resuscitation (CPR) may be necessary.
4. An individual who has received a known agent exposure or who exhibits definite signs or symptoms of agent exposure shall be injected immediately with the Nerve Agent Antidote Kit, MARK I.
1. Some of the early symptoms of a vapor exposure may be rhinorrhea (runny nose) and/or tightness in the chest with shortness of breath (bronchial construction).
2. Some of the early symptoms of a percutaneous exposure may be local muscular twitching or sweating at the area of exposure followed by nausea or vomiting.
3. Although myosis (pin-pointing of the pupils) may be an early sign of agent exposure, a Mark I Kit shall not be administered when myosis is the only sign present. Instead, the individual shall be taken immediately to the medical facility for observation.
4. Injections using the MARK I kit injectors (or atropine only if directed by the local physician) may be repeated at 5 to 20 minute intervals if signs and symptoms are progressing until three series of injections have been administered. No more injections will be given unless directed by medical personnel. In addition, a record will maintained of all injections given.
5. Administer, in rapid succession, all three MARK I kit injectors (or atropine if directed by the local physician) in the case of SEVERE signs of agent exposure.
CAUTION: The nerve Agent Antidote Kit, MARK I does not act as a prophylactic and shall not be administered until an agent exposure has been ascertained.
5. If indicated, CPR should be started immediately. Mouth-to-mouth resuscitation should be used when approved mask-bag or oxygen delivery systems are not available. Do not use mouth-to-mouth resuscitation when facial contamination exists.
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Re: United States Dual-Use Exports to Iraq and Their Impact
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Material Safety Data Sheet -- Lethal Nerve Agents Sulfur Mustards (HD and THD)
Section I: General Information
MANUFACTURER'S NAME: Department of the Army
MANUFACTURER'S ADDRESS:
U.S. Army Armament, Munitions and Chemical Command
Chemical Research, Development and Engineering Center
ATTN: SMCCR-CMS-E
Aberdeen Proving Ground, MD 21010-5423
CAS REGISTRY NUMBER: 505-60-2, 39472-40-7, 68157-62-0
CHEMICAL NAME AND SYNONYMS:
• Sulfide, bis (20chloroethyl)
• Bis (beta-chloroethyl) sulfide
• Bis (2-chloroethyl) sulfide
• (beta-chloroethylthio) ethane
• beta, beta'-dichlorodiethyl sulfide
• 2,2' dichlorodiethyl sulfide
• Di-2-chloroethyl sulfide
• beta, beta'-dichloroethyl sulfide
• 2,2'-dichloroethyl sulfide
TRADE NAME AND SYNONYMS:
• HD
• Senfgas
• H
• Sulfur mustard
• S-lost
• HS
• Iprit
• Suphur mustard gas
• Kampstoff "Lost"
• S-yperite
• Lost
• Yellow Cross Liquid
• Mustard Gas
• Yperite
CHEMICAL FAMILY: chlorinated sulfur compound
FORMULA: C4(H8)C12(S)
NFPA 704 SIGNAL:
• Health - 4
• Flammability - 1
• Reactivity - 1
Section II: Composition
INGREDIENTS FORMULA PERCENTAGE AIRBORNE
NAME BY WEIGHT EXPOSURE LIMIT (AEL)
Sulfur Mustard C4(H8)C12(S) 100 0.003 mg/m3 (8 hr-TWA)
Section III: Physical Data
BOILING POINT DEG F (DEG C): 422 DEG F. (217 DEG C)
VAPOR PRESSURE (mm Hg): 0.072 mm Hg @ 20 DEG C (0.11 mm Hg @ 25 DEG C)
VAPOR DENSITY (AIR=1): 5.5
SOLUBILITY IN WATER: Negligible. Soluble in acetone, CH3(C1), tetrachloroethane, ethylbenzoate, and ether.
SPECIFIC GRAVITY (H20=1): 1.27 @ 20 DEG C
VOLATILITY: 610 mg/m3 @ 20 DEG C; 920 mg/m3 @ 25 DEG C
APPEARANCE AND ODOR: Water clear if pure. Normally pale yellow to black. Slight garlic type odor. The odor threshold for HD is 0.0006 mg/m3
Section IV: Fire and Explosion Data
FLASHPOINT (METHOD USED): 105 DEG C (ignited by large explosive charges)
FLAMMABILITY LIMITS (% by volume): Unknown
EXTINGUISING MEDIA: Water, fog, foam, CO2. Avoid using extinguishing methods that will splash or spread mustard.
SPECIAL FIRE FIGHTING PROCEDURES:
All persons not engaged in extinguishing the fire should be immediately evacuated from the area. Fires involving HD should be contained to prevent contamination to uncontrolled areas. When responding to a fire alarm in buildings or areas containing agents, firefighting personnel should wear full firefighter protective clothing (without TAP clothing) during chemical agent firefighting and fire rescue operations.
Respiratory protection is required. Positive pressure, full facepiece, NIOSH-approved self contained breathing apparatus (SCBA) will be worn where there is danger of oxygen deficiency and when directed by the fire chief of chemical accident/incident (CAI) operations officer. The M9 or M17 series mask may be worn in lieu of SCBA when there is no danger of oxygen deficiency. In cases where firefighters are responding to a chemical accident/incident for rescue/reconnaissance purposes vice firefighting, they will wear appropriate levels of protective clothing (see Section 8).
Section V: Health Hazard Data
AIRBORNE EXPOSURE LIMIT (REL): The AEL for HD is 0.003 mg/m3 as proposed in the USAEHA Technical Guide No. 173, "Occupational Health Guidelines for the Evaluation and Control of Occupational Exposure to Mustard Agents H, HD and HT." No individual should be intentionally exposed to any direct skin or eye contact.
EFFECTS OF OVEREXPOSURE: HD is a vesicant (causing blisters) and alkylating agent producing cytotoxic action on the hematopoietic (blood-forming) tissues which are especially sensitive. The rate of detoxification of HD in the body is very slow and repeated exposures produce a cumulative effect. HD has been found to be a human carcinogen by the International Agency for Research on Cancer (IARC).
Median doses of HD in man are:
• LD50 (skin) = 100 mg/kg
• ICt50 (skin) = 2000 mg-min/m3 at 70-80 DEG F (humid environment); = 1000 mg-min/m3 at 90 DEG F (dry environment)
• ICt50 (eyes) = 200 mg-min/m3
• ICt50 (inhalation)=1500 mg-min/m3 (Ct unchanged with time)
• LD50 (oral) = 0.7 mg/kg
Maimum safe Ct for skin and eyes are 5 and 2 mg-min/m3, respectively.
ACUTE PHYSIOLOGICAL ACTION OF HD IS CLASSIFIED AS LOCAL AND SYSTEMIC:
• LOCALLY, HD affects both the eyes and the skin. SKIN damage occurs after percutaneous resorption. Being lipid soluble, HD can be resorbed into all organs. Skin penetration is rapid without skin irritation. Swelling (blisters) and reddening (erythema) of the skin occurs after a latency period of 4-24 hours following the exposure depending on degree of exposure and individual sensitivity. The skin healing process is very slow. Tender skin, mucous membrane and perspiration covered skin are more sensitive to the effects of HD. HD's effect on the skin, however, is less than on the eyes. Local action on the eyes produces severe necrotic damage and loss of eyesight. Exposure of eyes to HD vapor or aerosol produces lacrimation, photophobia, and inflammation of the conjunctiva and cornea.
• SYSTEMIC ACTIONS occur primarily through inhalation and ingestion. The HD vapor or aerosol is less toxic to the skin or eyes than the liquid form. When inhaled, the upper respiratory tract (nose, throat, trachea) is inflamed after a few hours latency period, accompanied by sneezing, coughing, and bronchitis, loss of appetite, diarrhea, fever, and apathy. Exposure to nearly lethal dose of HD can produce injury to bone marrow, lymph nodes, and spleen as indicated by a drop in WBC count and, therefore, results in increased susceptibilty to local and systemic infectons. Ingestion of HD will produce severe stomach pains, vomiting, and bloody stools after a 15-20 minute latency period.
• CHRONIC EXPOSURE to HD can cause sensitization, chronic lung impairment, (cough, shortness of breath, chest pain), and cancer of the mouth, throat, respiratory tract, skin, and leukemia. It may also cause birth defects.
EMERGENCY AND FIRST AID PROCEDURES:
• INHALATION: Remove from the source IMMEDIATELY. If breathing has stopped, give artificial respiration. If breathing is difficult, administer oxygen. Seek medical attention IMMEDIATELY.
• EYE CONTACT: Speed in decontaminating the eyes is absolutely essential. Remove person from the liquid source, flush the eyes immediately with water by tilting the head to the side, pulling the eyelids apart with the fingers and pouring water slowly into the eyes. Do not cover eyes with bandages but, if necessary, protect eyes by means of dark or opaque goggles. Transfer the patient to a medical facility IMMEDIATELY.
• SKIN CONTACT: Don respiratory protective mask and gloves; remove victim from agent source immediately. Flush skin and clothes with 5 percent solution of sodium hypochlorite or liquid house hold bleach within one minute. Cut and remove contaminated clothing, flush contaminated skin area again with 5 percent sodium hypochlorite solution, then wash contaminated skin area with soap and water. If shower facilities are available, wash thoroughly and transfer to medical facility. If the skin becomes contaminated with a thickened agent, blot/wipe the material off immediately with an absorbent pad/paper towel prior to using decontaminating solution.
• INGESTION: Do not induce vomiting. Give victim milk to drink. Seek medical attention immediately.
Section VI: Reactivity Data
STABILITY: Stable at ambient temperatures. Decomposition temperature is 149 DEG C to 177 DEG C. Mustard is a persistent agent depending on pH and moisture, and has been known to remain active for up to three years in soil.
INCOMPATIBILITY: Conditions to avoid. Rapidly corrosive to brass @ 65 DEG C. Will corrode steel at a rate of .0001 in. of steel per month @ 65 DEG C.
HAZARDOUS DECOMPOSITION PRODUCTS: Mustard will hydrolize to form HCI and thiodiglycol.
HAZARDOUS POLYMERIZATION: Will not occur.
Section VII: Spill, Leak and Disposal Procedures
STEPS TO BE TAKEN IN CASE MATERIAL IS RELEASED OR SPILLED: Only personnel in full protective clothing (see Section 8) will remain in area where mustard is spilled.
RECOMMENDED FIELD PROCEDURES:
The mustard should be contained using vermiculite, diatomaceious earth, clay or fine sand and neutralized as soon as possible using copious amounts of 5.25 percent Sodium Hypochlorite solution.
Scoop all material and place in an approved DOT container. Cover the contents of the drum with decontaminating solution as above. The exterior of the drum shall be decontaminated and then labeled IAW EPA and DOT regulations. All leaking containers shall be overpacked with vermiculite placed between the interior and exterior containers. Decontaminate and label IAW EPA and DOT regulations. Dispose of the material IAW waste disposal methods provided below. Dispose of the material used to decontaminate exterior of drum IAW Federal, state and local regulations. Conduct general area monitoring with an approved monitor (see Section 8) to confirm that the atmospheric concentrations do not exceed the airborne exposure limit (see Sections 2 and 8).
If 5.25 percent Sodium Hypochlorite solution is not available then the following decontaminants may be used instead and are listed in the order of preference: Calcium Hypochlorite Decontamination Solution No. 2 (DS2), and Super Tropical Bleach Slurry (STB). WARNING: Pure, undiluted Calcium Hypochlorite (HTH) will burn on contact with liquid blister agent.
RECOMMENDED LABORATORY PROCEDURES:
A minimum of 65 grams of decon per gram of HD is allowed to agitate for a minimum of one hour. Agitation is not necessary following the first hour if a single phase is obtained. At the end of 24 hours, the resulting solution shall be adjusted to a pH between 10 and 11. Test for presence of active chlorine by use of acidic potassium iodide solution to give free iodine color. Place 3 ml of the decontaminate in a test tube. Add several crystals of Potassium Iodine and swirl to dissolve. Add 3 ml of 50 wt percent Sulfuric Acid water and swirl. IMMEDIATE Iodine color indicates the presence of active chlorine. If negative, add additional 5.25 percent Sodium Hypochlorite solution to the decontamination solution, wait two hours, then test again for active chlorine. Continue procedure until positive chlorine is given by solution.
A 10 wt percent Calcium hypochlorite (HTH) mixture may be substituted for Sodium Hypochlorite. Use 65 grams of decon per gram of HD and continue the test as described for Sodium Hypochlorite.
Scoop up all material and place in approved DOT containers. Cover the contents of the drum with decontaminating solution as above. The exterior of the drum shall be decontaminated and then labeled IAW EPA and DOT regulations. All leaking containers shall be overpacked with vermiculite placed between the interior and exterior containers. Decontaminate and label IAW EPA and DOT regulations. Dispose of the material IAW waste disposal methods provided below. Dispose of the material used to decontaminate exterior of drum IAW federal, state and local regulations. Conduct general area monitoring with an approved monitor (see Section 8) to confirm that the atmospheric concentrations do not exceed the airborne exposure limits (see Section 8).
NOTE: Surfaces contaminated with HD and then rinse decontaminated may evolve sufficient mustard vapor to produce a physiological response.
WASTE DISPOSAL METHOD:
All decontaminated material should be collected, contained and chemically decontaminated or thermally decomposed in an EPA approved incinerator, which will filter or scrub toxic by-products from effluent air before discharge to the atmosphere. Any contaminated protective clothing should be decontaminated using HTH or bleach and analyzed to assure it is free of detectable contamination (3X) level. The clothing should then be sealed in plastic bags inside properly labeled drums and held for shipment back to the DA issue point. Decontamination of waste or excess material shall be accomplished in accordance with the procedures outlined above with the following exception:
HD on laboratory glassware may be oxidized by its vigorous reaction with concentrated nitric acid.
Open pit burning or burying of HD or items containing or contaminated with HD in any quantity is prohibited.
NOTE: Some states define decontaminated surety material as a RCRA Hazardous Waste.
Section VIII: Special Protection Informaton
RESPIRATORY PROTECTION:
Concentration mg/m3 Respiratory Protection/Emsemble Required
Less than or equal to 0.003 Protective mask not required provided that:
as an 8-hr TWA (a) Continuous real-time monitoring (with alarm
capability is conducted in the work area at the 0.003
mg/m3 level of detection.
(b) M9, M17 or M40 mask is available and donned if
ceiling concentrations exceed 0.003 mg/m3.
(c) Exposure has been limited to the extent practicable
by engineering controls (remote operations,
ventilation, and process isolation) or work
practices.
If these conditions are not met then the following applies:
Full facepiece, chemical canister, air purifying
respirators. (The M9, M17 or M40 series or other
certified equivalent masks are acceptable for this
purpose in conjunction with the M3 toxicological agent
protective (TAP) suit for dermal protection.)
Greater than 0.003 as an The Demilitarization Protective Ensemble (DPE), 30 mil,
8 hr TWA may be used with prior approval from the AMC Field
Safety Activity. Use time for the 30 mil DPE must be
restricted to two hours or less.
NOTE: When 30 mil DPE is not available the M9 or M40 series mask with Level A protective ensemble including impregnated innerwear can be used. However, use time shall be restricted to the extent operationally feasible, and may not exceed one hour.
As an additional precaution, the cuffs of the sleeves and the legs of the M3 suit shall be taped to the gloves and boots respectively to reduce aspiration.
VENTILATION:
Local Exhaust: Mandatory. Must be filtered or scrubbed.
Special: Chemical laboratory hoods shall have an average inward face velocity of 100 linear feet per minute (lfpm) plus or minus 10% with the velocity at any point not deviating from the average face velocity by more than 20%. Laboratory hoods shall be located such that cross- drafts do not exceed 20% of the inward face velocity. A visual performance test utilizing smoke-producing devices shall be performed in assessing the ability of the hood to contain agent HD.
Other: Recirculation of exhaust air from agent areas is prohibited. No connection between agent areas and other areas through ventilation system is permitted. Emergency backup power is necessary. Hoods should be tested semi-annually or after modificaton or maintenance operations. Operations should be performed 20 cm inside hoods.
PROTECTIVE GLOVES: MANDATORY. Butyl toxicological agent protective gloves (M3, M4, gloveset).
EYE PROTECTION: As a minimum, chemical goggles will be worn. For splash hazards use goggles and faceshield.
OTHER PROTECTIVE EQUIPMENT:
Full protective clothing will consist of the m3 butyl rubber suit with hood, M2A1 butyl boots, M3 gloves, impregnated underwear, M9 series mask and coveralls (if desired), or the Demilitarization Protective Ensemble (DPE). For general lab work. gloves and lab coat shall be worn with M9 or M17 mask readily available.
In addition, when handling contaminated lab animals, a daily clean smock, foot covers, and head covers are required.
MONITORING: Available monitoring equipment for agent HD is the M8/M9 Detector paper, blue bank tube, M256/M256A1 kits, bubbler. Depot Area Air Monitoring System (DAMMS), Automated Continuous Air Monitoring System (ACMS), CAM-M1, Hydrogen Flame Photometric Emission Detector (HYFED), and the Minature Chemical Agent Monitor (MINICAM).
Section IX: Special Precautions
PRECAUTIONS TO BE TAKEN IN HANDLING AND STORING:
During handling, the "buddy" (two-man) system will be used. Containers should be periodically inspected for leaks either visually or using a detector kit, and prior to transfering the containers from storage to work areas. Stringent control over all personnel handling HD must be exercised. Chemical showers, eyewash stations, and personal cleanliness facilities must be provided. Each worker will wash their hands before meals and shower thoroughly with special attention given to hair, face, neck, and hands, using plenty of soap before leaving at the end of the workday. No smoking, eating, or drinking is permitted at the work site.
Decontaminating equipment shall be conveniently located. Exits must be designed to permit rapid evacuation. HD should be stored in containers made of glass for Research, Development, Test and Evaluation (RDTE) quantities or one-ton steel containers for large quantities. Agent shall be double-contained in liquid-tight containers when in storage.
OTHER PRECAUTIONS: For additional information, see AMC-R 385-131, "Safety Regulations for Chemical Agents H, HD, HT, GB, and VX" and USAEHA Technical Guide No. 173, "Occupational Health Guidelines for the Evaluation and Control of Occupational Exposure to Mustard Agents H, HD, and HT."
Section X: Transportation Data
PROPER SHIPPING NAME: Poisonous liquid, n.o.s.
DOT HAZARD CLASSIFICATION: Poison A
DOT LABEL: Poison gas
DOT MARKING: Poisonous liquid, n.o.s. (Sulfide, bis 2-chloroethyl) NA 1955
DOT PLACARD: POISON GAS
EMERGENCY ACCIDENT PRECAUTIONS AND PROCEDURES: See Section IV, and VIII.
PRECAUTIONS TO BE TAKEN IN TRANSPORTATION:
Motor vehicles will be placarded regardless of quantity. Driver shall be given full and complete information regarding shipment and conditions in case of emergency. AR 50-6 deals specifically with the shipment of chemical agents. Shipments of agent will be escorted in accordance with AR 740-32.
While the Chemical Research Development and Engineering Center, Department of the Army believes that the data contained herein are factual and the opinions expressed are those of qualified experts regarding the results of the tests conducted, the data are not to be taken as a warranty or representation for which the Department of the Army or Chemical Research Development Engineering Center assumes legal responsibility. They are offered solely for your consideration, investigation, and verification. Any use of these data and information must be determined by the user to be in accordance with applicable Federal, State, and local laws and regulations.
Addendum A: Additional Information for Thickened HD
TRADE NAME AND SYNONYMS: Thickened HD, THD
HAZARDOUS INGREDIENTS: K125 (acryloid copolymer, 5%) is used to thicken HD, K125 is not known to be hazardous except in a finely-divided, powder form.
PHYSICAL DATA: Essentially the same as HD except for viscosity. The viscosity of HV is between 1000 and 1200 centistokes @ 25 DEG C.
FIRE AND EXPLOSION DATA: Same as HD.
HEALTH HAZARD DATA: Same as HD except for skin contact. For skin contact, don respiratory protective mask and remove contaminated clothing IMMEDIATELY. IMMEDIATELY scrape the HV from the skin surface, then wash the contaminated surface with acetone. Seek medical attention IMMEDIATELY.
SPILL, LEAK, AND DISPOSAL PROCEDURES:
If spills or leaks of HV occur, follow the same procedures as those for HD, but dissolve the THD in acetone prior to introducing any decontaminating solution. Containment of THD is generally not necessary. Spilled THD can be carefuly scraped off the contamininated surface and placed in a fully removable head drum with a high density, polyethylene lining. The THD can then be decontaminated, after it has been dissolved in acetone, using the same procedures used for HD. Contaminated surfaces should be treated with acetone, then decontaminated using the same procedures as those used for HD.
NOTE: Surfaces contaminated with THD or HD and then rinse-decontaminated may evolve sufficient mustard vapor to produce a physiological response.
SPECIAL PROTECTION INFORMATION: Same as HD.
SPECIAL PRECAUTIONS: Same as HD with the following addition. Handling the THD requires careful observation of the "stringers" (elastic, thread-like attachments) formed when the agents are transferred or dispensed. These stringers must be broken cleanly before moving the contaminating device or dispensing device to another location, or unwanted contamination of a working surface will result.
TRANSPORTATION DATA: Same as HD.
Section I: General Information
MANUFACTURER'S NAME: Department of the Army
MANUFACTURER'S ADDRESS:
U.S. Army Armament, Munitions and Chemical Command
Chemical Research, Development and Engineering Center
ATTN: SMCCR-CMS-E
Aberdeen Proving Ground, MD 21010-5423
CAS REGISTRY NUMBER: 505-60-2, 39472-40-7, 68157-62-0
CHEMICAL NAME AND SYNONYMS:
• Sulfide, bis (20chloroethyl)
• Bis (beta-chloroethyl) sulfide
• Bis (2-chloroethyl) sulfide
• (beta-chloroethylthio) ethane
• beta, beta'-dichlorodiethyl sulfide
• 2,2' dichlorodiethyl sulfide
• Di-2-chloroethyl sulfide
• beta, beta'-dichloroethyl sulfide
• 2,2'-dichloroethyl sulfide
TRADE NAME AND SYNONYMS:
• HD
• Senfgas
• H
• Sulfur mustard
• S-lost
• HS
• Iprit
• Suphur mustard gas
• Kampstoff "Lost"
• S-yperite
• Lost
• Yellow Cross Liquid
• Mustard Gas
• Yperite
CHEMICAL FAMILY: chlorinated sulfur compound
FORMULA: C4(H8)C12(S)
NFPA 704 SIGNAL:
• Health - 4
• Flammability - 1
• Reactivity - 1
Section II: Composition
INGREDIENTS FORMULA PERCENTAGE AIRBORNE
NAME BY WEIGHT EXPOSURE LIMIT (AEL)
Sulfur Mustard C4(H8)C12(S) 100 0.003 mg/m3 (8 hr-TWA)
Section III: Physical Data
BOILING POINT DEG F (DEG C): 422 DEG F. (217 DEG C)
VAPOR PRESSURE (mm Hg): 0.072 mm Hg @ 20 DEG C (0.11 mm Hg @ 25 DEG C)
VAPOR DENSITY (AIR=1): 5.5
SOLUBILITY IN WATER: Negligible. Soluble in acetone, CH3(C1), tetrachloroethane, ethylbenzoate, and ether.
SPECIFIC GRAVITY (H20=1): 1.27 @ 20 DEG C
VOLATILITY: 610 mg/m3 @ 20 DEG C; 920 mg/m3 @ 25 DEG C
APPEARANCE AND ODOR: Water clear if pure. Normally pale yellow to black. Slight garlic type odor. The odor threshold for HD is 0.0006 mg/m3
Section IV: Fire and Explosion Data
FLASHPOINT (METHOD USED): 105 DEG C (ignited by large explosive charges)
FLAMMABILITY LIMITS (% by volume): Unknown
EXTINGUISING MEDIA: Water, fog, foam, CO2. Avoid using extinguishing methods that will splash or spread mustard.
SPECIAL FIRE FIGHTING PROCEDURES:
All persons not engaged in extinguishing the fire should be immediately evacuated from the area. Fires involving HD should be contained to prevent contamination to uncontrolled areas. When responding to a fire alarm in buildings or areas containing agents, firefighting personnel should wear full firefighter protective clothing (without TAP clothing) during chemical agent firefighting and fire rescue operations.
Respiratory protection is required. Positive pressure, full facepiece, NIOSH-approved self contained breathing apparatus (SCBA) will be worn where there is danger of oxygen deficiency and when directed by the fire chief of chemical accident/incident (CAI) operations officer. The M9 or M17 series mask may be worn in lieu of SCBA when there is no danger of oxygen deficiency. In cases where firefighters are responding to a chemical accident/incident for rescue/reconnaissance purposes vice firefighting, they will wear appropriate levels of protective clothing (see Section 8).
Section V: Health Hazard Data
AIRBORNE EXPOSURE LIMIT (REL): The AEL for HD is 0.003 mg/m3 as proposed in the USAEHA Technical Guide No. 173, "Occupational Health Guidelines for the Evaluation and Control of Occupational Exposure to Mustard Agents H, HD and HT." No individual should be intentionally exposed to any direct skin or eye contact.
EFFECTS OF OVEREXPOSURE: HD is a vesicant (causing blisters) and alkylating agent producing cytotoxic action on the hematopoietic (blood-forming) tissues which are especially sensitive. The rate of detoxification of HD in the body is very slow and repeated exposures produce a cumulative effect. HD has been found to be a human carcinogen by the International Agency for Research on Cancer (IARC).
Median doses of HD in man are:
• LD50 (skin) = 100 mg/kg
• ICt50 (skin) = 2000 mg-min/m3 at 70-80 DEG F (humid environment); = 1000 mg-min/m3 at 90 DEG F (dry environment)
• ICt50 (eyes) = 200 mg-min/m3
• ICt50 (inhalation)=1500 mg-min/m3 (Ct unchanged with time)
• LD50 (oral) = 0.7 mg/kg
Maimum safe Ct for skin and eyes are 5 and 2 mg-min/m3, respectively.
ACUTE PHYSIOLOGICAL ACTION OF HD IS CLASSIFIED AS LOCAL AND SYSTEMIC:
• LOCALLY, HD affects both the eyes and the skin. SKIN damage occurs after percutaneous resorption. Being lipid soluble, HD can be resorbed into all organs. Skin penetration is rapid without skin irritation. Swelling (blisters) and reddening (erythema) of the skin occurs after a latency period of 4-24 hours following the exposure depending on degree of exposure and individual sensitivity. The skin healing process is very slow. Tender skin, mucous membrane and perspiration covered skin are more sensitive to the effects of HD. HD's effect on the skin, however, is less than on the eyes. Local action on the eyes produces severe necrotic damage and loss of eyesight. Exposure of eyes to HD vapor or aerosol produces lacrimation, photophobia, and inflammation of the conjunctiva and cornea.
• SYSTEMIC ACTIONS occur primarily through inhalation and ingestion. The HD vapor or aerosol is less toxic to the skin or eyes than the liquid form. When inhaled, the upper respiratory tract (nose, throat, trachea) is inflamed after a few hours latency period, accompanied by sneezing, coughing, and bronchitis, loss of appetite, diarrhea, fever, and apathy. Exposure to nearly lethal dose of HD can produce injury to bone marrow, lymph nodes, and spleen as indicated by a drop in WBC count and, therefore, results in increased susceptibilty to local and systemic infectons. Ingestion of HD will produce severe stomach pains, vomiting, and bloody stools after a 15-20 minute latency period.
• CHRONIC EXPOSURE to HD can cause sensitization, chronic lung impairment, (cough, shortness of breath, chest pain), and cancer of the mouth, throat, respiratory tract, skin, and leukemia. It may also cause birth defects.
EMERGENCY AND FIRST AID PROCEDURES:
• INHALATION: Remove from the source IMMEDIATELY. If breathing has stopped, give artificial respiration. If breathing is difficult, administer oxygen. Seek medical attention IMMEDIATELY.
• EYE CONTACT: Speed in decontaminating the eyes is absolutely essential. Remove person from the liquid source, flush the eyes immediately with water by tilting the head to the side, pulling the eyelids apart with the fingers and pouring water slowly into the eyes. Do not cover eyes with bandages but, if necessary, protect eyes by means of dark or opaque goggles. Transfer the patient to a medical facility IMMEDIATELY.
• SKIN CONTACT: Don respiratory protective mask and gloves; remove victim from agent source immediately. Flush skin and clothes with 5 percent solution of sodium hypochlorite or liquid house hold bleach within one minute. Cut and remove contaminated clothing, flush contaminated skin area again with 5 percent sodium hypochlorite solution, then wash contaminated skin area with soap and water. If shower facilities are available, wash thoroughly and transfer to medical facility. If the skin becomes contaminated with a thickened agent, blot/wipe the material off immediately with an absorbent pad/paper towel prior to using decontaminating solution.
• INGESTION: Do not induce vomiting. Give victim milk to drink. Seek medical attention immediately.
Section VI: Reactivity Data
STABILITY: Stable at ambient temperatures. Decomposition temperature is 149 DEG C to 177 DEG C. Mustard is a persistent agent depending on pH and moisture, and has been known to remain active for up to three years in soil.
INCOMPATIBILITY: Conditions to avoid. Rapidly corrosive to brass @ 65 DEG C. Will corrode steel at a rate of .0001 in. of steel per month @ 65 DEG C.
HAZARDOUS DECOMPOSITION PRODUCTS: Mustard will hydrolize to form HCI and thiodiglycol.
HAZARDOUS POLYMERIZATION: Will not occur.
Section VII: Spill, Leak and Disposal Procedures
STEPS TO BE TAKEN IN CASE MATERIAL IS RELEASED OR SPILLED: Only personnel in full protective clothing (see Section 8) will remain in area where mustard is spilled.
RECOMMENDED FIELD PROCEDURES:
The mustard should be contained using vermiculite, diatomaceious earth, clay or fine sand and neutralized as soon as possible using copious amounts of 5.25 percent Sodium Hypochlorite solution.
Scoop all material and place in an approved DOT container. Cover the contents of the drum with decontaminating solution as above. The exterior of the drum shall be decontaminated and then labeled IAW EPA and DOT regulations. All leaking containers shall be overpacked with vermiculite placed between the interior and exterior containers. Decontaminate and label IAW EPA and DOT regulations. Dispose of the material IAW waste disposal methods provided below. Dispose of the material used to decontaminate exterior of drum IAW Federal, state and local regulations. Conduct general area monitoring with an approved monitor (see Section 8) to confirm that the atmospheric concentrations do not exceed the airborne exposure limit (see Sections 2 and 8).
If 5.25 percent Sodium Hypochlorite solution is not available then the following decontaminants may be used instead and are listed in the order of preference: Calcium Hypochlorite Decontamination Solution No. 2 (DS2), and Super Tropical Bleach Slurry (STB). WARNING: Pure, undiluted Calcium Hypochlorite (HTH) will burn on contact with liquid blister agent.
RECOMMENDED LABORATORY PROCEDURES:
A minimum of 65 grams of decon per gram of HD is allowed to agitate for a minimum of one hour. Agitation is not necessary following the first hour if a single phase is obtained. At the end of 24 hours, the resulting solution shall be adjusted to a pH between 10 and 11. Test for presence of active chlorine by use of acidic potassium iodide solution to give free iodine color. Place 3 ml of the decontaminate in a test tube. Add several crystals of Potassium Iodine and swirl to dissolve. Add 3 ml of 50 wt percent Sulfuric Acid water and swirl. IMMEDIATE Iodine color indicates the presence of active chlorine. If negative, add additional 5.25 percent Sodium Hypochlorite solution to the decontamination solution, wait two hours, then test again for active chlorine. Continue procedure until positive chlorine is given by solution.
A 10 wt percent Calcium hypochlorite (HTH) mixture may be substituted for Sodium Hypochlorite. Use 65 grams of decon per gram of HD and continue the test as described for Sodium Hypochlorite.
Scoop up all material and place in approved DOT containers. Cover the contents of the drum with decontaminating solution as above. The exterior of the drum shall be decontaminated and then labeled IAW EPA and DOT regulations. All leaking containers shall be overpacked with vermiculite placed between the interior and exterior containers. Decontaminate and label IAW EPA and DOT regulations. Dispose of the material IAW waste disposal methods provided below. Dispose of the material used to decontaminate exterior of drum IAW federal, state and local regulations. Conduct general area monitoring with an approved monitor (see Section 8) to confirm that the atmospheric concentrations do not exceed the airborne exposure limits (see Section 8).
NOTE: Surfaces contaminated with HD and then rinse decontaminated may evolve sufficient mustard vapor to produce a physiological response.
WASTE DISPOSAL METHOD:
All decontaminated material should be collected, contained and chemically decontaminated or thermally decomposed in an EPA approved incinerator, which will filter or scrub toxic by-products from effluent air before discharge to the atmosphere. Any contaminated protective clothing should be decontaminated using HTH or bleach and analyzed to assure it is free of detectable contamination (3X) level. The clothing should then be sealed in plastic bags inside properly labeled drums and held for shipment back to the DA issue point. Decontamination of waste or excess material shall be accomplished in accordance with the procedures outlined above with the following exception:
HD on laboratory glassware may be oxidized by its vigorous reaction with concentrated nitric acid.
Open pit burning or burying of HD or items containing or contaminated with HD in any quantity is prohibited.
NOTE: Some states define decontaminated surety material as a RCRA Hazardous Waste.
Section VIII: Special Protection Informaton
RESPIRATORY PROTECTION:
Concentration mg/m3 Respiratory Protection/Emsemble Required
Less than or equal to 0.003 Protective mask not required provided that:
as an 8-hr TWA (a) Continuous real-time monitoring (with alarm
capability is conducted in the work area at the 0.003
mg/m3 level of detection.
(b) M9, M17 or M40 mask is available and donned if
ceiling concentrations exceed 0.003 mg/m3.
(c) Exposure has been limited to the extent practicable
by engineering controls (remote operations,
ventilation, and process isolation) or work
practices.
If these conditions are not met then the following applies:
Full facepiece, chemical canister, air purifying
respirators. (The M9, M17 or M40 series or other
certified equivalent masks are acceptable for this
purpose in conjunction with the M3 toxicological agent
protective (TAP) suit for dermal protection.)
Greater than 0.003 as an The Demilitarization Protective Ensemble (DPE), 30 mil,
8 hr TWA may be used with prior approval from the AMC Field
Safety Activity. Use time for the 30 mil DPE must be
restricted to two hours or less.
NOTE: When 30 mil DPE is not available the M9 or M40 series mask with Level A protective ensemble including impregnated innerwear can be used. However, use time shall be restricted to the extent operationally feasible, and may not exceed one hour.
As an additional precaution, the cuffs of the sleeves and the legs of the M3 suit shall be taped to the gloves and boots respectively to reduce aspiration.
VENTILATION:
Local Exhaust: Mandatory. Must be filtered or scrubbed.
Special: Chemical laboratory hoods shall have an average inward face velocity of 100 linear feet per minute (lfpm) plus or minus 10% with the velocity at any point not deviating from the average face velocity by more than 20%. Laboratory hoods shall be located such that cross- drafts do not exceed 20% of the inward face velocity. A visual performance test utilizing smoke-producing devices shall be performed in assessing the ability of the hood to contain agent HD.
Other: Recirculation of exhaust air from agent areas is prohibited. No connection between agent areas and other areas through ventilation system is permitted. Emergency backup power is necessary. Hoods should be tested semi-annually or after modificaton or maintenance operations. Operations should be performed 20 cm inside hoods.
PROTECTIVE GLOVES: MANDATORY. Butyl toxicological agent protective gloves (M3, M4, gloveset).
EYE PROTECTION: As a minimum, chemical goggles will be worn. For splash hazards use goggles and faceshield.
OTHER PROTECTIVE EQUIPMENT:
Full protective clothing will consist of the m3 butyl rubber suit with hood, M2A1 butyl boots, M3 gloves, impregnated underwear, M9 series mask and coveralls (if desired), or the Demilitarization Protective Ensemble (DPE). For general lab work. gloves and lab coat shall be worn with M9 or M17 mask readily available.
In addition, when handling contaminated lab animals, a daily clean smock, foot covers, and head covers are required.
MONITORING: Available monitoring equipment for agent HD is the M8/M9 Detector paper, blue bank tube, M256/M256A1 kits, bubbler. Depot Area Air Monitoring System (DAMMS), Automated Continuous Air Monitoring System (ACMS), CAM-M1, Hydrogen Flame Photometric Emission Detector (HYFED), and the Minature Chemical Agent Monitor (MINICAM).
Section IX: Special Precautions
PRECAUTIONS TO BE TAKEN IN HANDLING AND STORING:
During handling, the "buddy" (two-man) system will be used. Containers should be periodically inspected for leaks either visually or using a detector kit, and prior to transfering the containers from storage to work areas. Stringent control over all personnel handling HD must be exercised. Chemical showers, eyewash stations, and personal cleanliness facilities must be provided. Each worker will wash their hands before meals and shower thoroughly with special attention given to hair, face, neck, and hands, using plenty of soap before leaving at the end of the workday. No smoking, eating, or drinking is permitted at the work site.
Decontaminating equipment shall be conveniently located. Exits must be designed to permit rapid evacuation. HD should be stored in containers made of glass for Research, Development, Test and Evaluation (RDTE) quantities or one-ton steel containers for large quantities. Agent shall be double-contained in liquid-tight containers when in storage.
OTHER PRECAUTIONS: For additional information, see AMC-R 385-131, "Safety Regulations for Chemical Agents H, HD, HT, GB, and VX" and USAEHA Technical Guide No. 173, "Occupational Health Guidelines for the Evaluation and Control of Occupational Exposure to Mustard Agents H, HD, and HT."
Section X: Transportation Data
PROPER SHIPPING NAME: Poisonous liquid, n.o.s.
DOT HAZARD CLASSIFICATION: Poison A
DOT LABEL: Poison gas
DOT MARKING: Poisonous liquid, n.o.s. (Sulfide, bis 2-chloroethyl) NA 1955
DOT PLACARD: POISON GAS
EMERGENCY ACCIDENT PRECAUTIONS AND PROCEDURES: See Section IV, and VIII.
PRECAUTIONS TO BE TAKEN IN TRANSPORTATION:
Motor vehicles will be placarded regardless of quantity. Driver shall be given full and complete information regarding shipment and conditions in case of emergency. AR 50-6 deals specifically with the shipment of chemical agents. Shipments of agent will be escorted in accordance with AR 740-32.
While the Chemical Research Development and Engineering Center, Department of the Army believes that the data contained herein are factual and the opinions expressed are those of qualified experts regarding the results of the tests conducted, the data are not to be taken as a warranty or representation for which the Department of the Army or Chemical Research Development Engineering Center assumes legal responsibility. They are offered solely for your consideration, investigation, and verification. Any use of these data and information must be determined by the user to be in accordance with applicable Federal, State, and local laws and regulations.
Addendum A: Additional Information for Thickened HD
TRADE NAME AND SYNONYMS: Thickened HD, THD
HAZARDOUS INGREDIENTS: K125 (acryloid copolymer, 5%) is used to thicken HD, K125 is not known to be hazardous except in a finely-divided, powder form.
PHYSICAL DATA: Essentially the same as HD except for viscosity. The viscosity of HV is between 1000 and 1200 centistokes @ 25 DEG C.
FIRE AND EXPLOSION DATA: Same as HD.
HEALTH HAZARD DATA: Same as HD except for skin contact. For skin contact, don respiratory protective mask and remove contaminated clothing IMMEDIATELY. IMMEDIATELY scrape the HV from the skin surface, then wash the contaminated surface with acetone. Seek medical attention IMMEDIATELY.
SPILL, LEAK, AND DISPOSAL PROCEDURES:
If spills or leaks of HV occur, follow the same procedures as those for HD, but dissolve the THD in acetone prior to introducing any decontaminating solution. Containment of THD is generally not necessary. Spilled THD can be carefuly scraped off the contamininated surface and placed in a fully removable head drum with a high density, polyethylene lining. The THD can then be decontaminated, after it has been dissolved in acetone, using the same procedures used for HD. Contaminated surfaces should be treated with acetone, then decontaminated using the same procedures as those used for HD.
NOTE: Surfaces contaminated with THD or HD and then rinse-decontaminated may evolve sufficient mustard vapor to produce a physiological response.
SPECIAL PROTECTION INFORMATION: Same as HD.
SPECIAL PRECAUTIONS: Same as HD with the following addition. Handling the THD requires careful observation of the "stringers" (elastic, thread-like attachments) formed when the agents are transferred or dispensed. These stringers must be broken cleanly before moving the contaminating device or dispensing device to another location, or unwanted contamination of a working surface will result.
TRANSPORTATION DATA: Same as HD.
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Re: United States Dual-Use Exports to Iraq and Their Impact
by admin » Thu Dec 17, 2015 10:03 pm
Material Safety Data Sheet -- Sulfur Mustard (HT)
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Re: United States Dual-Use Exports to Iraq and Their Impact
by admin » Fri Dec 18, 2015 3:26 am
103D Congress
2d Session
SENATE
U.S. CHEMICAL AND BIOLOGICAL WARFARE-RELATED DUAL USE EXPORTS TO IRAQ AND THEIR POSSIBLE IMPACT ON THE HEALTH CONSEQUENCES OF THE PERSIAN GULF WAR
COMMITTEE STAFF REPORT (No. 3)
TO
CHAIRMAN DONALD W. RIEGLE, JR.
OF THE
COMMITTEE ON BANKING, HOUSING AND URBAN AFFAIRS
WITH RESPECT TO
EXPORT ADMINISTRATION:
CHEMICAL WARFARE AGENT IDENTIFICATION, CHEMICAL INJURIES, AND OTHER FINDINGS
UNITED STATES SENATE
October 7, 1994
THIS REPORT IS DERIVED ENTIRELY FROM UNCLASSIFIED SOURCES
APPROVED FOR PUBLIC RELEASE
UNLIMITED DISTRIBUTION IS AUTHORIZED
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